Epoxide and fluorinated epoxide stabilizers for fluoroolefins

ABSTRACT

The present invention relates to compositions comprising at least one fluoroolefin and an effective amount of stabilizer that may be an epoxide, fluorinated epoxide or oxetane, or a mixture thereof with other stabilizers. The stabilized compositions may be useful in cooling apparatus, such as refrigeration, air-conditioning, chillers, and heat pumps, as well as in applications as foam blowing agents, solvents, aerosol propellants, fire extinguishants, and sterilants.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to compositions comprising at least onefluoroolefin and a stabilizer. The stabilized compositions may be usefulin cooling systems as replacements for existing refrigerants with higherglobal warming potential.

2. Description of Related Art

New environmental regulations on working fluids have forced therefrigeration and air-conditioning industry to look for new workingfluids with low global warming potential (GWP).

Replacement working fluids are being sought that have low GWP, notoxicity, non-flammability, reasonable cost and excellent refrigerationperformance.

Fluoroolefins have been proposed as working fluids alone or in mixtures.However, it has been observed that fluoroolefins can exhibit degradationwhen exposed to high temperatures or when contacted with other compounds(e.g., moisture, oxygen, or other compounds with which they may undergocondensation reactions. This degradation may occur when fluoroolefinsare used as working fluids in heat transfer equipment (refrigeration orair-conditioning equipment, for instance) or when used in some otherapplication. This degradation may occur by any number of differentmechanisms. In one instance, the degradation may be caused byinstability of the compounds at extreme temperatures. In otherinstances, the degradation may be caused by oxidation in the presence ofair that has inadvertently leaked into the system. Whatever the cause ofsuch degradation, because of the instability of the fluoroolefins, itmay not be practical to incorporate these fluoroolefins intorefrigeration or air-conditioning systems. Therefore, to take advantageof the many other attributes of fluoroolefins, means to reduce thedegradation is needed.

SUMMARY OF THE INVENTION

The present disclosure provides a composition comprising at least onefluoroolefin and an effective amount of a stabilizer comprising:

-   -   a. at least one compound selected from the group consisting of        epoxides and fluorinated epoxides represented by Formula A,        wherein each of R² through R⁵ is H, alkyl of 1 to 6 carbon atoms        or fluoroalkyl of 1 to 6 carbon atoms with the proviso that at        least one of R² through R⁵ is a fluoroalkyl group;

-   -   and    -   b. at least one compound selected from the group consisting of        thiophosphates, butylated triphenylphosphorothionates, organo        phosphates, fullerenes, aryl alkyl ether, functionalized        perfluoropolyethers, polyoxyalkylated aromatics, alkylated        aromatics, oxetanes, ascorbic acid, thiols, lactones,        thioethers, amines, nitromethane, alkylsilanes, benzophenone        derivatives, aryl sulfides, divinyl terephthalate, diphenyl        terephthalate, and mixtures thereof.

Also provided is a composition comprising:

-   -   a. at least one fluoroolefin; and    -   b. an effective amount of a stabilizer comprising:        -   i) at least one epoxide, fluorinated epoxide or mixture            thereof;        -   ii) at least one phosphite, phenol, terpene, terpenoid, or            mixture thereof; and        -   iii) at least one metal deactivator selected from the group            consisting of areoxalyl bis(benzylidene)hydrazide;            N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine);            2,2′-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate);            N,N′-(disalicyclidene)-1,2-propanediamine;            ethyenediaminetetraacetic acid and salts thereof; triazoles;            benzotriazole, 2-mercaptobenzothiazole, tolutriazole            derivatives, N,N-disalicylidene-1,2-diaminopropane, and            mixtures thereof.

Also provided is a method for stabilizing a composition comprising atleast one fluoroolefin, said method comprising adding an effectiveamount of a stabilizer comprising at least one epoxide or fluorinatedepoxide and at least one compound selected from the group consisting ofthiophosphates, butylated triphenylphosphorothionates, organophosphates, fullerenes, aryl alkyl ether, functionalizedperfluoropolyethers, polyoxyalkylated aromatics, alkylated aromatics,oxetanes, ascorbic acid, thiols, lactones, thioethers, amines,nitromethane, alkylsilanes, benzophenone derivatives, aryl sulfides,divinyl terephthalate, diphenyl terephthalate, and mixtures thereof.

Also provided is a method for reducing degradation of a compositioncomprising at least one fluoroolefin, wherein said degradation is causedby the presence of inadvertent air in a refrigeration, air-conditioningor heat pump system, said method comprising adding an effective amountof a stabilizer comprising at least one epoxide or fluorinated epoxideand at least one compound selected from the group consisting ofthiophosphates, butylated triphenylphosphorothionates, organophosphates, fullerenes, aryl alkyl ether, functionalizedperfluoropolyethers, polyoxyalkylated aromatics, alkylated aromatics,oxetanes, ascorbic acid, thiols, lactones, thioethers, amines,nitromethane, alkylsilanes, benzophenone derivatives, aryl sulfides,divinyl terephthalate, diphenyl terephthalate, and mixtures thereof tothe composition comprising at least one fluoroolefin.

Also provided is a method for reducing reaction with oxygen for acomposition comprising at least one fluoroolefin, said method comprisingadding an effective amount of a stabilizer comprising at least oneepoxide or fluorinated epoxide and at least one compound selected fromthe group consisting of thiophosphates, butylatedtriphenylphosphorothionates, organo phosphates, fullerenes, aryl alkylether, functionalized perfluoropolyethers, polyoxyalkylated aromatics,alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalate, diphenylterephthalate, and mixtures thereof to the composition comprising atleast one fluoroolefin.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a composition comprising at least onefluoroolefin and an effective amount of a stabilizer comprising: a. atleast one epoxide or fluorinated epoxide.

These compositions have a variety of utilities in working fluids, whichinclude use as These compositions have a variety of utilities in workingfluids, which include use as foaming agents, blowing agents, fireextinguishing agents, heat transfer mediums (such as heat transferfluids and refrigerants for use in refrigeration systems, refrigerators,air conditioning systems, heat pumps, chillers, and the like), to name afew.

A blowing agent is a volatile composition that expands a polymer matrixto form a cellular structure.

A solvent is a fluid that removes a soil from a substrate, or deposits amaterial onto a substrate, or carries a material.

An aerosol propellant is a volatile composition of one or morecomponents that exerts a pressure greater than one atmosphere to expel amaterial from a container.

A fire extinguishant is a volatile composition that extinguishes orsuppresses a flame.

A sterilant is a volatile biocidal fluid or blend containing a volatilebiocidal fluid that destroys a biologically active material or the like.

A heat transfer medium (also referred to herein as a heat transferfluid, a heat transfer composition or a heat transfer fluid composition)is a working fluid used to carry heat from a heat source to a heat sink.

A refrigerant is a compound or mixture of compounds that function as aheat transfer fluid in a cycle wherein the fluid undergoes a phasechange from a liquid to a gas and back.

The term fluoroolefins, as used herein, describes compounds whichcomprise carbon atoms, fluorine atoms, and optionally hydrogen atoms. Inone embodiment, the fluoroolefins used in the compositions of thepresent invention comprise compounds with 2 to 12 carbon atoms. Inanother embodiment the fluoroolefins comprise compounds with 3 to 10carbon atoms, and in yet another embodiment the fluoroolefins comprisecompounds with 3 to 7 carbon atoms. Representative fluoroolefins includebut are not limited to all compounds as listed in Table 1, Table 2, andTable 3.

One embodiment of the present invention provides fluoroolefins havingthe formula E- or Z—R¹CH═CHR² (Formula I), wherein R¹ and R² are,independently, C₁ to C₆ perfluoroalkyl groups. Examples of R¹ and R²groups include, but are not limited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂,CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃,CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, andC(CF₃)₂CF₂C₂F₅. In one embodiment the fluoroolefins of Formula I have atleast about 4 carbon atoms in the molecule. In another embodiment, thefluoroolefins of Formula I have at least about 5 carbon atoms in themolecule. Exemplary, non-limiting Formula I compounds are presented inTable 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iECF₃CH═CHCF₂CF—(CF₃)₂1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene F14sECF₃CH═CHCF(CF₃)—C₂F₅1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene F14tECF₃CH═CHC(CF₃)₃1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23EC₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iEC₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-eneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept- 2-ene F15tECF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2- ene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-eneF24iE C₂F₅CH═CHCF₂CF—(CF₃)₂1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept- 3-ene F24sEC₂F₅CH═CHCF(CF₃)—C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept- 3-ene F24tEC₂F₅CH═CHC(CF₃)₃1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3- ene F33EC₂F₅CF₂CH═CH—CF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE(CF₃)₂CFCH═CH—CF(CF₃)₂1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3- ene F33iEC₂F₅CF₂CH═CH—CF(CF₃)₂1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept- 3-ene F16ECF₃CH═CH(CF₂)₅CF₃1,1,1,4,4,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-2-ene F16sECF₃CH═CHCF(CF₃)(CF₂)₂C₂F₅ 1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-ene F16tE CF₃CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25EC₂F₅CH═CH(CF₂)₄CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iEC₂F₅CH═CHCF₂CF₂CF(CF₃)₂ 1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-ene F25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,6,6,7,7,7-decafluoro-5,5- bis(trifluoromethyl)hept-3-ene F34EC₂F₅CF₂CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iEC₂F₅CF₂CH═CH—CF₂CF(CF₃)₂ 1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-ene F34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6- (trifluoromethyl)oct-4-eneF34tE C₂F₅CF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene F3i4E (CF₃)₂CFCH═CH—(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro- 2(trifluoromethyl)oct-3-eneF3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂ 1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene F3i4sE (CF₃)₂CFCH═CH—CF(CF₃)C₂F₅1,1,1,2,5,6,6,7,7,7-decafluoro-2,5- bis(trifluoromethyl)hept-3-eneF3i4tE (CF₃)₂CFCH═CH—C(CF₃)₃1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3- ene F26EC₂F₅CH═CH(CF₂)₅CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec- 3-ene F26sEC₂F₅CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene F26tE C₂F₅CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5- bis(trifluoromethyl)oct-3-eneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec- 4-ene F35iEC₂F₅CF₂CH═CH— 1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-CF₂CF₂CF(CF₃)₂ (trifluoromethyl)non-4-ene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6- bis(trifluoromethyhoct-4-eneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene F3i5iE (CF₃)₂CFCH═CH—1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7- CF₂CF₂CF(CF₃)₂bis(trifluoromethyl)oct-3-ene F3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5- tris(trifluoromethyl)hept-3-ene F44ECF₃(CF₂)₃CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec- 5-ene F44iECF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene F44sE CF₃(CF₂)₃CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene F44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,- bis(trifluoromethyl)oct-3-eneF4i4iE (CF₃)₂CFCF₂CH═CH— 1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-CF₂CF(CF₃)₂ bis(trifluoromethyl)oct-4-ene F4i4sE (CF₃)₂CFCF₂CH═CH—1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6- CF(CF₃)C₂F₅bis(trifluoromethyl)oct-4-ene F4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6- tris(trifluoromethyl)hept-3-eneF4s4sE C₂F₅CF(CF₃)CH═CH— 1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-CF(CF₃)C₂F₅ bis(trifluoromethyl)oct-4-ene F4s4tEC₂F₅CF(CF₃)CH═CH—C(CF₃)₃ 1,1,1,6,6,6-hexafluoro-2,2,5,5-tris(trifluoromethyl)hept-3-ene F4t4tE (CF₃)₃CCH═CH—C(CF₃)₃1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5- tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹I with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂. Said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include fabricated from stainlesssteels, in particular of the austenitic type, and the well-known highnickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickelbased alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may take be conducted in semi-batch mode inwhich the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefinshould be between about 1:1 to about 4:1, preferably from about 1.5:1 to2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1adduct as reported by Jeanneaux, et al. in Journal of FluorineChemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide withsaid perfluoroalkyltrihydroolefin are preferably within the range ofabout 150° C. to 300° C., preferably from about 170° C. to about 250°C., and most preferably from about 180° C. to about 230° C. Suitablecontact times for the reaction of the perfluoroalkyl iodide with theperfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours,preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or may preferably be recoveredand purified by distillation prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting thetrihydroiodoperfluoroalkane with a basic substance. Suitable basicsubstances include alkali metal hydroxides (e.g., sodium hydroxide orpotassium hydroxide), alkali metal oxide (for example, sodium oxide),alkaline earth metal hydroxides (e.g., calcium hydroxide), alkalineearth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, ormixtures of basic substances such as soda lime. Preferred basicsubstances are sodium hydroxide and potassium hydroxide. Said contactingof the trihydroiodoperfluoroalkane with a basic substance may take placein the liquid phase preferably in the presence of a solvent capable ofdissolving at least a portion of both reactants. Solvents suitable forthe dehydroiodination step include one or more polar organic solventssuch as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol,n-butanol, isobutanol, and tertiary butanol), nitriles (e.g.,acetonitrile, propionitrile, butyronitrile, benzonitrile, oradiponitrile), dimethyl sulfoxide, N,N-dimethylformamide,N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend onthe boiling point product and the ease of separation of traces of thesolvent from the product during purification. Typically, ethanol orisopropanol are good solvents for the reaction.

Typically, the dehydroiodination reaction may be carried out by additionof one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction may be fabricated from glass, ceramic, ormetal and is preferably agitated with an impeller or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about10° C. to about 100° C., preferably from about 20° C. to about 70° C.The dehydroiodination reaction may be carried out at ambient pressure orat reduced or elevated pressure. Of note are dehydroiodination reactionsin which the compound of Formula I is distilled out of the reactionvessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted bycontacting an aqueous solution of said basic substance with a solutionof the trihydroiodoperfluoroalkane in one or more organic solvents oflower polarity such as an alkane (e.g., hexane, heptane, or octane),aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g.,methylene chloride, chloroform, carbon tetrachloride, orperchloroethylene), or ether (e.g., diethyl ether, methyl tert-butylether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane,dimethoxyethane, diglyme, or tetraglyme) in the presence of a phasetransfer catalyst. Suitable phase transfer catalysts include quaternaryammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammoniumhydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammoniumchloride, and tricaprylylmethylammonium chloride), quaternaryphosphonium halides (e.g., triphenylmethylphosphonium bromide andtetraphenylphosphonium chloride), or cyclic polyether compounds known inthe art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in theabsence of solvent by adding the trihydroiodoperfluoroalkane to a solidor liquid basic substance.

Suitable reaction times for the dehydroiodination reactions are fromabout 15 minutes to about six hours or more depending on the solubilityof the reactants. Typically the dehydroiodination reaction is rapid andrequires about 30 minutes to about three hours for completion. Thecompound of formula I may be recovered from the dehydroiodinationreaction mixture by phase separation after addition of water, bydistillation, or by a combination thereof.

In another embodiment of the present invention, fluoroolefins comprisecyclic fluoroolefins (cyclo-[CX═CY(CZW)_(n)-] (Formula II), wherein X,Y, Z, and W are independently selected from H and F, and n is an integerfrom 2 to 5). In one embodiment the fluoroolefins of Formula II, have atleast about 3 carbon atoms in the molecule. In another embodiment, thefluoroolefins of Formula II have at least about 4 carbon atoms in themolecule. In yet another embodiment, the fluoroolefins of Formula IIhave at least about 5 carbon atoms in the molecule. Representativecyclic fluoroolefins of Formula II are listed in Table 2.

TABLE 2 Cyclic fluoroolefins Structure Chemical name FC-C1316cccyclo-CF₂CF₂ 1,2,3,3,4,4- CF═CF— hexafluorocyclobutene HFC-C1334cccyclo-CF₂ 3,3,4,4-tetrafluorocyclobutene CF₂CH═CH— HFC-C1436 cyclo-3,3,4,4,5,5,- CF₂CF₂CF₂ hexafluorocyclopentene CH═CH— FC-C1418y cyclo-1,2,3,3,4,4,5,5- CF₂CF═ octafluorocyclopentene CFCF₂CF₂— FC-C151-10ycyclo-CF₂CF═ 1,2,3,3,4,4,5,5,6,6- CFCF₂CF₂CF₂— decafluorocyclohexene

The compositions of the present invention may comprise a single compoundof Formula I or formula II, for example, one of the compounds in Table 1or Table 2, or may comprise a combination of compounds of Formula I orformula II.

In another embodiment, fluoroolefins may comprise those compounds listedin Table 3.

TABLE 3 Name Structure Chemical name HFC-1225ye CF₃CF═CHF1,2,3,3,3-pentafluoro-1-propene HFC-1225zc CF₃CH═CF₂1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF₂CF═CF₂1,1,2,3,3-pentafluoro-1-propene HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF₃CF═CH₂2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF₃CH═CHF1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH₂FCF═CF₂1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF₂CH═CF₂1,1,3,3-tetrafluoro-1-propene HFC-1243yf CHF₂CF═CH₂2,3,3-trifluoro-1-propene HFC-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propeneHFC-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFC-1243zc CH₂FCH═CF₂1,1,3-trifluoro-1-propene HFC-1243ye CH₂FCF═CHF1,2,3-trifluoro-1-propene HFC-1243ze CHF₂CH═CHF1,3,3-trifluoro-1-propene FC-1318my CF₃CF═CFCF₃1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF₃CF₂CF═CF₂1,1,2,3,3,4,4,4-octafluoro-1-butene HFC-1327my CF₃CF═CHCF₃1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF═CFCF₂CF₃1,2,3,3,4,4,4-heptafluoro-1-butene HFC-1327py CHF₂CF═CFCF₃1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF₃)₂C═CHF1,3,3,3-tetrafluoro-2- (trifluoromethyl)-1-propene HFC-1327czCF₂═CHCF₂CF₃ 1,1,3,3,4,4,4-heptafluoro-1-butene HFC-1327cye CF₂═CFCHFCF₃1,1,2,3,4,4,4-heptafluoro-1-butene HFC-1327cyc CF₂═CFCF₂CHF₂1,1,2,3,3,4,4-heptafluoro-1-butene HFC-1336yf CF₃CF₂CF═CH₂2,3,3,4,4,4-hexafluoro-1-butene HFC-1336ze CHF═CHCF₂CF₃1,3,3,4,4,4-hexafluoro-1-butene HFC-1336eye CHF═CFCHFCF₃1,2,3,4,4,4-hexafluoro-1-butene HFC-1336eyc CHF═CFCF₂CHF₂1,2,3,3,4,4-hexafluoro-1-butene HFC-1336pyy CHF₂CF═CFCHF₂1,1,2,3,4,4-hexafluoro-2-butene HFC-1336qy CH₂FCF═CFCF₃1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF₂CH═CFCF₃1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF₃CH═CFCHF₂1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF₂═CFCF₂CH₂F1,1,2,3,3,4-hexafluoro-1-butene HFC-1336pe CF₂═CFCHFCHF₂1,1,2,3,4,4-hexafluoro-1-butene HFC-1336ft CH₂═C(CF₃)₂3,3,3-trifluoro-2-(trifluoromethyl)-1- propene HFC-1345qz CH₂FCH═CFCF₃1,1,1,2,4-pentafluoro-2-butene HFC-1345mzy CF₃CH═CFCH₂F1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF₃CF₂CH═CH₂3,3,4,4,4-pentafluoro-1-butene HFC-1345mzz CHF₂CH═CHCF₃1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH₃CF═CFCF₃1,1,1,2,3-pentafluoro-2-butene HFC-1345fyc CH₂═CFCF₂CHF₂2,3,3,4,4-pentafluoro-1-butene HFC-1345pyz CHF₂CF═CHCHF₂1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH₃CF₂CF═CF₂1,1,2,3,3-pentafluoro-1-butene HFC-1345pyy CH₂FCF═CFCHF₂1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH₂FCF₂CF═CF₂1,2,3,3,4-pentafluoro-1-butene HFC-1345ctm CF₂═C(CF₃)(CH₃)1,1,3,3,3-pentafluoro-2-methyl-1- propene HFC-1345ftp CH₂═C(CHF₂)(CF₃)2-(difluoromethyl)-3,3,3-trifluoro-1- propene HFC1345fye CH₂═CFCHFCF₃2,3,4,4,4-pentafluoro-1-butene HFC-1345eyf CHF═CFCH₂CF₃1,2,4,4,4-pentafluoro-1-butene HFC-1345eze CHF═CHCHFCF₃1,3,4,4,4-pentafluoro-1-butene HFC-1345ezc CHF═CHCF₂CHF₂1,3,3,4,4-pentafluoro-1-butene HFC-1345eye CHF═CFCHFCHF₂1,2,3,4,4-pentafluoro-1-butene HFC-1354fzc CH₂═CHCF₂CHF₂3,3,4,4-tetrafluoro-1-butene HFC-1354ctp CF₂═C(CHF₂)(CH₃)1,1,3,3-tetrafluoro-2-methyl-1- propene HFC-1354etm CHF═C(CF₃)(CH₃)1,3,3,3-tetrafluoro-2-methyl-1- propene HFC-1354tfp CH₂═C(CHF₂)₂2-(difluoromethyl)-3,3-difluoro-1- propene HFC-1354my CF₃CF═CHCH₃1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH₃CF═CHCF₃1,1,1,3-tetrafluoro-2-butene FC-141-10myy CF₃CF═CFCF₂CF₃1,1,1,2,3,4,4,5,5,5-decafluoro-2- pentene FC-141-10cy CF₂═CFCF₂CF₂CF₃1,1,2,3,3,4,4,5,5,5-decafluoro-1- pentene HFC-1429mzt (CF₃)₂C═CHCF₃1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene HFC-1429myzCF₃CF═CHCF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-2- pentene HFC-1429mzyCF₃CH═CFCF₂CF₃ 1,1,1,3,4,4,5,5,5-nonafluoro-2- pentene HFC-1429eycCHF═CFCF₂CF₂CF₃ 1,2,3,3,4,4,5,5,5-nonafluoro-1- pentene HFC-1429czcCF₂═CHCF₂CF₂CF₃ 1,1,3,3,4,4,5,5,5-nonafluoro-1- pentene HFC-1429cyccCF₂═CFCF₂CF₂CHF₂ 1,1,2,3,3,4,4,5,5-nonafluoro-1- pentene HFC-1429pyyCHF₂CF═CFCF₂CF₃ 1,1,2,3,4,4,5,5,5-nonafluoro-2- pentene HFC-1429myycCF₃CF═CFCF₂CHF₂ 1,1,1,2,3,4,4,5,5-nonafluoro-2- pentene HFC-1429myyeCF₃CF═CFCHFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-2- pentene HFC-1429eyymCHF═CFCF(CF₃)₂ 1,2,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-buteneHFC-1429cyzm CF₂═CFCH(CF₃)₂ 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene HFC-1429mzt CF₃CH═C(CF₃)₂1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene HFC-1429czymCF₂═CHCF(CF₃)₂ 1,1,3,4,4,4-hexafluooro-3- (trifluoromethyl)-1-buteneHFC-1438fy CH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1- penteneHFC-1438eycc CHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1- penteneHFC-1438ftmc CH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1438czzm CF₂═CHCH(CF₃)₂1,1,4,4,4-pentafluoro-3- (trifluoromethyl)-1-butene HFC-1438ezymCHF═CHCF(CF₃)₂ 1,3,4,4,4-pentafluoro-3- (trifluoromethyl)-1-buteneHFC-1438ctmf CF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1447fzy (CF₃)₂CFCH═CH₂3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447fzCF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1-pentene HFC-1447fyccCH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1-pentene HFC-1447czcfCF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1-pentene HFC-1447mytmCF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3-methyl- 2-buteneHFC-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFC-1447ezz CHF═CHCH(CF₃)₂1,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447qztCH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-2- (trifluoromethyl)-2-buteneHFC-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-butene HFC-1456szt (CF₃)₂C═CHCH₃3-(trifluoromethyl)-4,4,4-trifluoro-2- butene HFC-1456szy CF₃CF₂CF═CHCH₃3,4,4,5,5,5-hexafluoro-2-pentene HFC-1456mstz CF₃C(CH₃)═CHCF₃1,1,1,4,4,4-hexafluoro-2-methyl-2- butene HFC-1456fzce CH₂═CHCF₂CHFCF₃3,3,4,5,5,5-hexafluoro-1-pentene HFC-1456ftmf CH₂═C(CF₃)CH₂CF₃4,4,4-trifluoro-2-(trifluoromethyl)-1- butene FC-151-12c CF₃(CF₂)₃CF═CF₂1,1,2,3,3,4,4,5,5,6,6,6- dodecafluoro-1-hexene (or perfluoro-1-hexene)FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃ 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (or perfluoro-3-hexene) FC-151-12mmtt(CF₃)₂C═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene FC-151-12mmzz (CF₃)₂CFCF═CFCF₃1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl)-2-penteneHFC-152-11mmtz (CF₃)₂C═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene HFC-152-11mmyyz (CF₃)₂CFCF═CHCF₃1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-pentene PFBECF₃CF₂CF₂CF₂CH═CH₂ 3,3,4,4,5,5,6,6,6-nonafluoro-1- (or HFC-1549fz)hexene (or perfluorobutylethylene) HFC-1549fztmm CH₂═CHC(CF₃)₃4,4,4-trifluoro-3,3- bis(trifluoromethyl)-1-butene HFC-1549mmtts(CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene HFC-1549fycz CH₂═CFCF₂CH(CF₃)₂2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl)-1-pentene HFC-1549mytsCF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-3- methyl-2-penteneHFC-1549mzzz CF₃CH═CHCH(CF₃)₂ 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene HFC-1558szy CF₃CF₂CF₂CF═CHCH₃3,4,4,5,5,6,6,6-octafluoro-2-hexene HFC-1558fzccc CH₂═CHCF₂CF₂CF₂CHF₂3,3,4,4,5,5,6,6-octafluoro-2-hexene HFC-1558mmtzc (CF₃)₂C═CHCF₂CH₃1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-pentene HFC-1558ftmfCH₂═C(CF₃)CH₂C₂F₅ 4,4,5,5,5-pentafluoro-2- (trifluoromethyl)-1-penteneHFC-1567fts CF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene HFC-1567szz CF₃CF₂CF₂CH═CHCH₃4,4,5,5,6,6,6-heptafluoro-2-hexene HFC-1567fzfc CH₂═CHCH₂CF₂C₂F₅4,4,5,5,6,6,6-heptafluoro-1-hexene HFC-1567sfyy C F₃CF₂CF═CFC₂H₅1,1,1,2,2,3,4-heptafluoro-3-hexene HFC-1567fzfy CH₂═CHCH₂CF(CF₃)₂4,5,5,5-tetrafluoro-4- (trifluoromethyl)-1-pentene HFC-1567myzzmCF₃CF═CHCH(CF₃)(CH₃) 1,1,1,2,5,5,5-heptafluoro-4-methyl- 2-penteneHFC-1567mmtyf (CF₃)₂C═CFC₂H₅ 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene FC-161-14myy CF₃CF═CFCF₂CF₂C₂F₅1,1,1,2,3,4,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene FC-161-14mcyyCF₃CF₂CF═CFCF₂C₂F₅ 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene HFC-162-13mzy CF₃CH═CFCF₂CF₂C₂F₅1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene HFC162-13myzCF₃CF═CHCF₂CF₂C₂F₅ 1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-hepteneHFC-162-13mczy CF₃CF₂CH═CFCF₂C₂F₅ 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene HFC-162-13mcyz CF₃CF₂CF═CHCF₂C₂F₅1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene PEVE CF₂═CFOCF₂CF₃pentafluoroethyl trifluorovinyl ether PMVE CF₂═CFOCF₃ trifluoromethyltrifluorovinyl ether

The compounds listed in Table 2 and Table 3 are available commerciallyor may be prepared by processes known in the art or as described herein.

1,1,1,4,4-pentafluoro-2-butene may be prepared from1,1,1,2,4,4-hexafluorobutane (CHF₂CH₂CHFCF₃) by dehydrofluorination oversolid KOH in the vapor phase at room temperature. The synthesis of1,1,1,2,4,4-hexafluorobutane is described in U.S. Pat. No. 6,066,768,incorporated herein by reference.

1,1,1,4,4,4-hexafluoro-2-butene may be prepared from1,1,1,4,4,4-hexafluoro-2-iodobutane (CF₃CHICH₂CF₃) by reaction with KOHusing a phase transfer catalyst at about 60° C. The synthesis of1,1,1,4,4,4-hexafluoro-2-iodobutane may be carried out by reaction ofperfluoromethyl iodide (CF₃I) and 3,3,3-trifluoropropene (CF₃CH═CH₂) atabout 200° C. under autogenous pressure for about 8 hours.

3,4,4,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorinationof 1,1,1,2,2,3,3-heptafluoropentane (CF₃CF₂CF₂CH₂CH₃) using solid KOH orover a carbon catalyst at 200-300° C. 1,1,1,2,2,3,3-heptafluoropentanemay be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene(CF₃CF₂CF₂CH═CH₂).

1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,3,3,4-heptafluorobutane (CH₂FCF₂CHFCF₃) using solid KOH.

1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,2,4,4-heptafluorobutane (CHF₂CH₂CF₂CF₃) using solid KOH.

1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4,4-heptafluorobutane (CF₃CH₂CF₂CHF₂) using solid KOH.

1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,2,2,3-hexafluorobutane (CH₂FCH₂CF₂CF₃) using solid KOH.

1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4-hexafluorobutane (CF₃CH₂CF₂CH₂F) using solid KOH.

1,1,1,3-tetrafluoro-2-butene may be prepared by reacting1,1,1,3,3-pentafluorobutane (CF₃CH₂CF₂CH₃) with aqueous KOH at 120° C.

1,1,1,4,4,5,5,5-octafluoro-2-pentene may be prepared from(CF₃CHICH₂CF₂CF₃) by reaction with KOH using a phase transfer catalystat about 60° C. The synthesis of4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out by reactionof perfluoroethyliodide (CF₃CF₂I) and 3,3,3-trifluoropropene at about200° C. under autogenous pressure for about 8 hours.

1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF₃CF₂CHICH₂CF₂CF₃) byreaction with KOH using a phase transfer catalyst at about 60° C. Thesynthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane may be carriedout by reaction of perfluoroethyliodide (CF₃CF₂I) and3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂) at about 200° C. underautogenous pressure for about 8 hours.

1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be preparedby the dehydrofluorination of1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane(CF₃CHICH₂CF(CF₃)₂) with KOH in isopropanol. CF₃CHICH₂CF(CF₃)₂ is madefrom reaction of (CF₃)₂CFI with CF₃CH═CH₂ at high temperature, such asabout 200° C.

1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reactionof 1,1,1,4,4,4-hexafluoro-2-butene (CF₃CH═CHCF₃) withtetrafluoroethylene (CF₂═CF₂) and antimony pentafluoride (SbF₅).

2,3,3,4,4-pentafluoro-1-butene may be prepared by dehydrofluorination of1,1,2,2,3,3-hexafluorobutane over fluorided alumina at elevatedtemperature.

2,3,3,4,4,5,5,5-ocatafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solidKOH.

1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane overfluorided alumina at elevated temperature.

Many of the compounds of Formula I, Formula II, Table 1, Table 2, andTable 3 exist as different configurational isomers or stereoisomers.When the specific isomer is not designated, the present invention isintended to include all single configurational isomers, singlestereoisomers, or any combination thereof. For instance, F11E is meantto represent the E-isomer, Z-isomer, or any combination or mixture ofboth isomers in any ratio. As another example, HFC-1225ye is meant torepresent the E-isomer, Z-isomer, or any combination or mixture of bothisomers in any ratio.

The present invention provides a composition comprising at least onefluoroolefin and an effective amount of a stabilizer comprising: a. atleast one epoxide or fluorinated epoxide; and b. at least one compoundselected from the group consisting of thiophosphates, butylatedtriphenylphosphorothionates, organophosphates, fullerenes, aryl alkylether, functionalized perfluoropolyethers, polyoxyalkylated aromatics,alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalate, diphenylterephthalate, and mixtures thereof.

In one embodiment, the stabilizers of the present invention comprise atleast one epoxide. Epoxides include 1,2-propylene oxide (CAS reg. no.[75-56-9]), 1,2-butylene oxide (CAS reg. no. [106-88-7]),butylphenylglycidy ether, pentylphenylglycidyl ether,hexylphenylglycidyl ether, heptylphenylglycidyl ether,octylphenylglycidyl ether, nonylphenylglycidyl ether,decylphenylglycidyl ether, glycidyl methylphenylether, 1,4-glycidylphenyl diether, 4-methoxyphenylglycidyl ether, naphthyl glycidyl ether,1,4-diglycidyl naphthyl diether, butylphenyl glycidyl ether, n-butylglycidyl ether, isobutyl glycidyl ether, hexanediol diglycidyl ether,allyl glycidyl ether, polypropylene glycol diglycidyl ether, andmixtures thereof.

In another embodiment, the stabilizers of the present invention compriseat least one fluorinated epoxide. The fluorinated epoxide stabilizers ofthe present invention may be depicted by Formula A, wherein each of R²through R⁵ is H, alkyl of 1 to 6 carbon atoms or fluoroalkyl of 1 to 6carbon atoms with the proviso that at least one of R² through R⁵ is afluoroalkyl group.

Representative fluorinated epoxide stabilizers include but are notlimited to trifluoromethyloxirane and 1,1-bis(trifluoromethyl)oxirane.Such compounds may be prepared by methods known in the art, for instanceby methods described in, Journal of Fluorine Chemistry, volume 24, pages93-104 (1984), Journal of Ormanic Chemistry, volume 56, pages 3187 to3189 (1991), and Journal of Fluorine Chemistry, volume 125, pages 99-105(2004).

The composition of the present invention additionally comprise acompound selected from a different class of compounds. This additionalstabilizer is selected from the group consisting of thiophosphates,butylated triphenylphosphorothionates, organophosphates, fullerenes,functionalized perfluoropolyethers, polyoxyalkylated aromatics,alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalate, and diphenylterephthalate, and mixtures thereof, meaning mixtures of any of thestabilizers listed in this paragraph, and in addition, mixtures of anystabilizer or combination of stabilizers listed in this paragraph withany of the stabilizers or combination of the epoxide or fluorinatedepoxide stabilizers described above.

In one embodiment, the stabilizers of the present invention comprise atleast one thiophosphate. The thiophosphate stabilizers of the presentinvention are compounds derived from phosphoric acids by substitutingdivalent sulfur for one or more oxygen atoms. These may bemonothiophosphates, dithiophosphates or higher order. A representativedithiophosphate is commercially available from Ciba Specialty Chemicalsof Basel, Switzerland (hereinafter “Ciba”) under the trademark Irgalube®63. In another embodiment, thiophosphates include dialkylthiophosphateesters. A representative dialkylthiophosphate ester stabilizer iscommercially available from Ciba under the trademark Irgalube® 353.

In another embodiment, the stabilizers of the present invention compriseat least one butylated triphenylphosphorothionate as depicted by FormulaB.

An example of a butylated triphenylphosphorothionate, wherein each R isindependently selected from H or tert-butyl, is commercially availablefrom Ciba under the trademark Irgalube® 232.

In another embodiment, the stabilizers of the present invention compriseat least one organophosphate. The organophosphate stabilizers includebut are not limited to amine phosphates, trialkyl phosphates, triarylphosphates, mixed alkyl-aryl phosphates (alkyldiaryl, dialkylaryl oralkylated aryl), and cyclic phosphates. A representative amine phosphateis commercially available from Ciba under the trademark Irgalube® 349.Representative trialkyl phosphates include: trimethyl phosphate((CH₃)₃PO₄, Cas reg. no. 512-56-1); triethyl phosphate ((CH₃CH₂)₃PO₄,Cas reg. no. 78-40-0); tributyl phosphate ((C₄H₉)₃PO₄, CAS reg. no.126-73-8); trioctyl phosphate((C₈H₁₇)₃PO₄. CAS reg. no. 1806-54-8); andtri(2-ethylhexyl)phosphate ((CH₃CH(C₂H₅)(CH₂)₄)₃PO₄. CAS reg. no.78-42-2). Representative triaryl phosphates include: triphenyl phosphate((C₆H₅O)₃PO, CAS reg. no. 115-86-6); tricresyl phosphate (TCP,(CH₃C₆H₄O)₃PO, CAS reg. no. 1330-78-5); and trixylenyl phosphate(((CH₃)₂CeH₃O)₃PO, CAS reg. no. 25155-23-1). Representative mixedalkyl-aryl phosphates include: isopropylphenyl phenyl phosphate (IPPP,(C₆H₅O)₂((CH₃)₂CHO)PO, CAS reg. no. 68782-95-6) and bis(t-butylphenyl)phenyl phosphate (TBPP, (CeH₅O)₂((CH₃)₃C)PO, CAS reg. no. 65652-41-7).Such phosphorus compounds are available from multiple chemical supplierssuch as Aldrich (Milwaukee, Wisconsin); Alfa Aesar (Ward Hill, MA); orAkzo Nobel (Arnhem, the Netherlands). Representative commerciallyavailable alkylated triaryl phosphates include a butylated triphenylphosphate, commercially available from Akzo Nobel (Amhem, theNetherlands) under the trademark Syn-O-Ad® 8784; a tert-butylatedtriphenyl phosphate commercially available from Great Lakes ChemicalCorporation (GLCC, West Lafayette, IN) under the trademark Durad® 620;and iso-propylated triphenyl phosphates, also commercially availablefrom GLCC under the trademarks Durad® 220 and 110.

In another embodiment, the stabilizers of the present invention compriseat least one fullerene. Fullerenes are closed carbon cages that arebonded as hexagonal carbon rings (benzene) linked to each other partlyvia pentagons. The relationship between the number of apices (a, carbonatoms) and hexagon carbon rings (n) (pentagon rings always number 12) isgiven by: a=2(n+10). While this formula provides for all theoreticalstructures, only those molecules with relatively low stress anddistortion will be stable. Representative fullerenes include but are notlimited to Buckminsterfullerene (C60, or “bucky ball”, CAS reg. no.[99685-96-8]), and [5,6]fullerene-C₇₀ (C70, CAS reg. no. [115383-22-7]),fullerene-C₇₆ (CAS reg. no. [135113-15-4]), fullerene-C₇₈ (CAS reg. no.[136316-32-0]), and fullerene-C₈₄ (CAS reg. no. [135113-16-5]).

In another embodiment, the stabilizers of the present invention compriseat least one aryl alkyl ether. The aryl alkyl ether stabilizers of thepresent invention may be depicted by Formula C, wherein n is 1, 2 or 3and R¹ is an alkyl group of 1 to 16 carbon atoms.

Representative aryl alkyl ethers include but are not limited to anisole,1,4-dimethoxybenzene, 1,4-diethoxybenzene and 1,3,5-trimethoxybenzene.

In another embodiment, the stabilizers of the present invention compriseat least one functionalized perfluoropolyether. Such functionalizedperfluoropolyethers may be perfluoropolyether- orperfluoroalkyl-containing and phosphorus-containing partially esterifiedaryl phosphates, aryl phosphonates and salts thereof, containing either(i) a mono- or poly-alkylene oxide linking group between the phosphorusand a fluorocarbon group, or (ii) no linking group between thephosphorus and fluorocarbon group as described in U.S. Pat. No.6,184,187, and references therein.

In another embodiment, the functionalized perfluoropolyether stabilizersmay be compounds as represented by Formula C above, which contain eithera perfluoroalkyl or perfluoropolyether side chain. Further, thefunctionalized perfluoropolyether stabilizers may be perfluoropolyetheralkyl alcohols comprising a perfluoropolyether segment and one or morealcohols segments having a general formula, —CH₂(C_(q)H_(2q))OH,wherein-C_(q)H_(2q) represents a divalent linear or branched alkylradical where q is an integer from 1 to about 10 as described in U.S.patent application Ser. No. 11/156,348, filed Jun. 17, 2005.

In another embodiment, the functionalized perfluoropolyether stabilizersof the present invention may comprise substituted aryl pnictogencompositions having the structure [R_(f)¹—(C_(t)R_((u+v)))]_(m)E(O)_(n)(C_(t)R¹ _((u+v+1)))_((3-m)), wherein

R_(f)1 is a fluoropolyether chain having a formula weight ranging fromabout 400 to about 15,000, comprises repeat units, and is selected fromthe group consisting of:

-   -   (a) J-O—(CF(CF₃)CF₂O)_(c)(CFXO)_(d)CFZ—;    -   (b) J¹-O—(CF₂CF₂O)_(e)(CF₂O)_(f)CFZ¹—;    -   (c) J²-O—(CF(CF₃)CF₂O)_(j)CF(CF₃)CF₂—;    -   (d) J³-O—(CQ₂-CF₂CF₂—O)_(k)—CQ₂-CF₂—;    -   (e) J³-O—(CF(CF₃)CF₂O)_(g)(CF₂CF₂O)_(h)(CFXO)_(i)—CFZ—;    -   (f) J⁴-O—(CF₂CF₂O)_(r)CF₂—; and    -   (h) combinations of two or more thereof        wherein    -   J is a fluoroalkyl group selected from the group consisting of        CF₃, C₂F₅, C₃F₇, CF₂Cl, C₂F₄Cl, C₃F₆Cl, and combinations of two        or more thereof;    -   c and d are numbers such that the ratio of c:d ranges from about        0.01 to about 0.5;    -   X is F, CF₃, or combinations thereof;    -   Z is F, Cl or CF₃;    -   J¹ is a fluoroalkyl group selected from the group consisting of        CF₃, C₂F₅, C₃F₇, CF₂Cl, C₂F₄Cl, and combinations of two or more        thereof;    -   e and f are numbers such that the ratio of e:f ranges from about        0.3 to about 5;    -   Z¹ is F or Cl;    -   J² is C₂F₅, C₃F₇, or combinations thereof;    -   j is an average number such that the formula weight of R_(f)        ranges from about 400 to about 15,000;    -   J³ is selected from the group consisting of CF₃, C₂F₅, C₃F₇, and        combinations of two or more thereof;    -   k is an average number such that the formula weight of R_(f)        ranges from about 400 to about 15,000;    -   each Q is independently F, Cl, or H;    -   g, h and i are numbers such that (g+h) ranges from about 1 to        about 50, the ratio of i:(g+h) ranges from about 0.1 to about        0.5;    -   J⁴ is CF₃, C₂F₅, or combinations thereof;    -   r is an average number such that the formula weight of R_(f)        ranges from about 400 to about 15,000; and    -   each R and R¹ is independently H, a C₁-C₁₀ alkyl, a halogen,        OR³, OH, SO₃M, NR² ₂, R³OH, R³SO₃M, R³NR² ₂, R³NO₂, R³CN,        C(O)OR³, C(O)OM, C(O)R³, or C(O)NR² ₂, or combinations of two or        more thereof;        wherein    -   R² is independently H, C₁-C₁₀ alkyl, or combinations of two or        more thereof;    -   R³ is a C₁-C₁₀ alkyl; and    -   M is hydrogen or a metal, preferably not aluminum;    -   t is equal to (6+u);    -   u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16;    -   v is independently either 2 or 4;    -   n is 0 or 1;    -   E is P, As, or Sb; and    -   m is greater than about 0.5 to about 3, provided that, when E=P,        m=3.0 and t=6, R cannot be exclusively H or contain F; as        described in U.S. patent application Ser. No. 11/167,330, filed        Jun. 27, 2006.

In another embodiment, the functionalized perfluoropolyether stabilizersof the present invention may comprise aryl perfluoropolyethers, whichare monofunctional aryl perfluoropolyethers having the formula ofR_(f)—(Y)_(a)—(C_(t)R_((u+v)))—(O—C_(t)R¹ _((u+v)))_(b)—R, difunctionalaryl perfluoropolyethers having the formula of R_(f)¹—[(Y)_(a)—(C_(t)R_((u+v)))—(O—C_(t)R¹ _((u+V)))_(b)—R]₂, orcombinations thereof, wherein

-   -   each of R_(f) and R_(f) ¹ has a formula weight of about 400 to        about 15,000;    -   R_(f) comprises repeat units selected from the group consisting        of    -   (a) J-O—(CF(CF₃)CF₂O)_(c)(CFXO)_(d)CFZ—,    -   (b) J¹-O—(CF₂CF₂O)_(e)(CF₂O)_(f)CFZ¹—,    -   (c) J²-O—(CF(CF₃)CF₂O)_(j)CF(CF₃)—,    -   (d) J³-O—(CQ₂-CF₂CF₂—O)_(k)—CQ₂-,    -   (e) J³O—(CF(CF₃)CF₂O)_(g)(CF₂CF₂O)_(h)(CFX—O)_(i)—CFZ—,    -   (f) J⁴-O—(CF₂CF₂O)_(k)—CF₂—, and    -   (g) combinations of two or more thereof; and    -   where    -   the units with formulae CF₂CF₂O and CF₂O are randomly        distributed along the chain;    -   J is CF₃, C₂F₅, C₃F₇, CF₂Cl, C₂F₄Cl, C₃F₆Cl, or combinations of        two or more thereof;    -   c and d are numbers such that the c/d ratio ranges from about        0.01 to about 0.5;    -   X is —F, —CF₃, or combinations thereof;    -   Z is —F, —Cl or —CF₃;    -   Z¹ is —F or —Cl,    -   J¹ is CF₃, C₂F₅, C₃F₇, CF₂Cl, C₂F₄Cl, or combinations of two or        more thereof;    -   e and f are numbers such that the e/f ratio ranges from about        0.3 to about 5;    -   J² is —C₂F₅, —C₃F₇, or combinations thereof;    -   j is an average number such that the formula weight of R_(f)        ranges from about 400 to about 15,000;    -   J³ is CF₃, C₂F₅, C₃F₇, or combinations of two or more thereof;    -   k is an average number such that the formula weight of R_(f)        ranges from about 400 to about 15,000;    -   each Q is independently —F, —Cl, or —H;    -   g, h and i are numbers such that (g+h) ranges from about 1 to        about 50, the i/(g+h) ratio ranges from about 0.1 to about 0.5;    -   J⁴ is CF₃, C₂F₅, or combinations thereof;    -   k′ is an average number such that the formula weight of R_(f)        ranges from about 400 to about 15,000;    -   each R is independently —H, a halogen, —OH, —SO₃M, NR³ ₂, —NO₂,        —R⁴OH, —R⁴SO₃M, —R⁴NR³ ₂, —R⁴NO₂, —R⁴CN, —C(O)OR⁴, —C(O)OM,        —C(O)R⁴, —C(O)NR³ ₂, or combinations of two or more thereof;        except that when b=0, R cannot be four hydrogen atoms and —OH,        or —Br, or —NH₂; or R cannot be solely H or —NO₂, or        combinations thereof;    -   each R¹ is independently H, —R⁴, —OR⁴, a halogen, —OH, —SO₃M,        —NR³ ₂, —NO₂, —CN, —R⁴OH, —R⁴SO₃M, —R⁴NR³ ₂, —R⁴NO₂, —R⁴CN,        —C(O)OR⁴, —C(O)OM, —C(O)R⁴, C(O)NR³ ₂, or combinations of two or        more thereof provided that if b=0, the combination of R and R²        cannot be four or more hydrogen atoms and —OH, —Br, —NH₂, or        —NO₂;    -   each R³ is independently H, C₁-C₁₀ alkyl, or combinations of two        or more thereof;    -   R⁴ is a C₁-C₁₀ alkyl;    -   M is a hydrogen or metal ion;    -   a is 0 or 1;    -   b is 0-5;    -   Y is a divalent radical —CH₂OCH₂, —(CH₂)_(o)—O—, —(CF₂)_(n)—,        —CF₂O—, —CF₂OCF₂—, —C(O)—, —C(S)—, or combinations of two or        more thereof;    -   n is about 1 to about 5;    -   is about 2 to about 5;    -   t is equal to 6+u;    -   u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16;    -   v is independently either 2 or 4;    -   Rf¹ is —(CF₂CF₂O)_(e)(CF₂O)_(f)CF₂—,        —(C₃F₆O)_(p)(CF₂CF₂O)_(q)(CFXO)_(r)CF₂—,        —(CF₂CF₂O)(C₃F₆O)_(w)CF(CF₃)—,        —CF(CF₃)O(C₃F₆O)_(w)—Rf²—O(C₃F₆O)_(w)CF(CF₃)—,        —((CQ₂)CF₂CF₂O)_(s)CF₂CF₂—, or combinations of two or more        thereof;    -   where    -   e, f, X, and Q are as defined above;    -   p, q and r are numbers such that (p+q) ranges from 1 to 50 and        r/(p+q) ranges from 0.1 to 0.05;    -   each w is independently 2 to 45;    -   Rf² is linear or branched —C_(m)F_(2m)—;        -   m is 1-10; and    -   s is an average number such that the formula weight of R_(f) ¹        ranges from 400 to 15,000, as described in U.S. patent        application Ser. No. 11/218,259, filed Sep. 1, 2005.

In another embodiment, the stabilizer may comprise at least onepolyoxyalkylated aromatic. The polyoxyalkylated aromatics are compoundsrepresented by Formula C wherein the R¹ group is a polyoxyalkylatedgroup comprising at least one —CH₂CH₂O— moiety. In another embodiment,the stabilizers of the present invention comprise at least one alkylatedaromatic compound. Representative alkylated aromatics include but arenot limited to alkylbenzene lubricants, both branched and linear, suchas Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenes sold byShriéve Chemicals) and HAB 22 (branched alkylbenzene sold by NipponOil).

In another embodiment, the stabilizers of the present invention compriseat least one oxetane. The oxetane stabilizers of the present inventionmay be a compound with one or more oxetane groups and is represented byFormula D, wherein R₁-R₆ are the same or different and can be selectedfrom hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.

Representative oxetane stabilizers include but are not limited to3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd);3-ethyl-3-((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co.,Ltd); and 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, such as OXT-212(Toagosei Co., Ltd).

In another embodiment, the stabilizers of the present invention compriseascorbic acid (CAS reg. no. [50-81-7]).

In another embodiment, the stabilizers of the present invention compriseat least one thiol. Thiol compounds, also known as mercaptans orhydrosulfides, are the sulfur analogs of the hydroxyl group containingalcohols. Representative thiol stabilizers include but are not limitedto methanethiol (methyl mercaptan), ethanethiol (ethyl mercaptan),Coenzyme A (CAS reg. no. [85-61-0]), dimercaptosuccinic acid (DMSA, CASreg. no. [2418-14-6]), grapefruit mercaptan((R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol, CAS reg. no.[83150-78-1]), cysteine ((R)-2-amino-3-sulfanyl-propanoic acid, CAS reg.no. [52-90-4]), and lipoamide (1,2-dithiolane-3-pentanamide, CAS reg.no. [940-69-2].

In another embodiment, the stabilizers of the present invention compriseat least one lactones. Lactones are cyclic esters that may be producedby the reaction of an alcohol group with a carboxylic acid group in thesame molecule. Representative lactone stabilizers of the presentinvention include but are not limited to gamma-butyrolactone (CAS reg.no. [96-48-0]), delta-gluconolactone (CAS reg. no. [90-80-2]),gamma-undecalactone (CAS reg. no. [104-67-6]),6,7-dihydro-4(5H)-benzofuranone (CAS reg. No. [16806-93-2]), and5,7-bis(1,1-dimethylethyl)-3-[2,3(or3,4)-dimethylphenyl]-2(3H)-benzofuranone (CAS reg. no [201815-03-4])such as Irganox® HP-136 (Ciba).

In another embodiment, the stabilizers of the present invention compriseat least one thioether. Thioether stabilizers of the present inventioninclude but are not limited to benzyl phenyl sulfide (CAS reg. no.[831-91-4]), diphenyl sulfide (CAS reg. no. [139-66-2]), commerciallyavailable from Ciba under the trademark Irganox® PS 802 (Ciba) anddidodecyl 3,3′-thiopropionate, commercially available from Ciba underthe trademark Irganox® PS 800 (Ciba), and mixtures thereof, meaningmixtures of any of the thioethers listed in this paragraph.

In another embodiment, the stabilizers of the present invention compriseat least one amine. In one embodiment the amine stabilizers comprise atleast one compound selected from the group consisting of triethylamine,tributylamine, diisopropylamine, triisopropylamine, triisobutylamine,p-phenylenediamine, and diphenylamine. In another embodiment, the aminestabilizers comprise dialkylamines including(N-(1-methylethyl)-2-propylamine, CAS reg. no. [108-18-9]). In anotherembodiment the amine stabilizers include hindered amine antioxidants.Hindered amine antioxidants include amines derived from substitutedpiperidine compounds, in particular derivatives of an alkyl-substitutedpiperidyl, piperidinyl, piperazinone, or alkoxypiperidinyl compounds.Representative hindered amine antioxidants include2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol;bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate (CAS reg. no.[41556-26-7]); di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, such as thehindered amine commercially available under the trademark Tinuvin® 770by Ciba; poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidylsuccinate (CAS reg. no. [65447-77-0]), such as that commerciallyavailable under the trademark Tinuvin® 622LD from Ciba; alkylatedparaphenylenediamines, such asN-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine, orN,N′-di-sec-butyl-p-phenylenediamine; and hydroxylamines such as tallowamines or N-methylbis(hydrogenated tallow alkyl)amine. Some otherhindered amine antioxidants include the amine antioxidant commerciallyavailable from Ciba under the trademark Tinuvin® 765, or commerciallyavailable from Mayzo, Inc. under the trademark BLS® 1944 and BLS® 1770.The amines also include mixtures of any of the amines listed in thisparagraph.

In another embodiment, the stabilizers of the present invention comprisenitromethane (CH₃NO₂, CAS reg. no. [75-52-5]).

In another embodiment, the stabilizers of the present invention compriseat least one alkyl silane. Silanes are compounds similar to hydrocarbonswherein a silicon atom replaces each carbon. Alkyl silane stabilizersinclude but are not limited to bis(dimethylamino)methylsilane (DMAMS,CAS reg. no. [22705-33-5]), tris(trimethylsilyl)silane (TTMSS, CAS reg.no. [1873-77-4]), vinyltriethoxysilane (VTES, CAS reg. no. [78-08-0]),and vinyltrimethoxysilane (VTMO, CAS reg. no. [2768-02-7]).

In another embodiment, the stabilizers of the present invention compriseat least one benzophenone derivative. Benzophenone derivativestabilizers comprise benzophenone that may be substituted with sidegroups including halides, such as fluorine, chlorine, bromine or iodine,amino groups, hydroxyl groups, alkyl groups such as methyl, ethyl orpropyl groups, aryl groups such as phenyl, nitro groups, or anycombinations of such groups. Representative benzophenone derivativestabilizers include but are not limited to: 2,5-difluorobenzophenone;2′,5′-dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone;2-fluorobenzophenone; 2-hydroxybenzophenone; 2-methylbenzophenone;2-amino-4′-chlorobenzophenone; 2-amino-4′-fluorobenzophenone;2-amino-5-bromo-2′-chlorobenzophenone; 2-amino-5-chlorobenzophenone;2-amino-5-chloro-2′-fluorobenzophenone; 2-amino-5-nitrobenzophenone;2-amino-5-nitro-2′-chlorobenzophenone;2-amino-2′,5-dichlorobenzophenone; 2-chloro-4′-fluorobenzophenone;2-hydroxy-4-methoxybenzophenone; 2-hydroxy-5-chlorobenzophenone;2-methylamino-5-chlorobenzophenone; 3-methylbenzophenone;3-nitrobenzophenone; 3-nitro-4′-chloro-4-fluorobenzophenone;4-chlorobenzophenone; 4-fluorobenzophenone; 4-hydroxybenzophenone;4-methoxybenzophenone; 4-methylbenzophenone; 4-nitrobenzophenone;4-phenylbenzophenone; 4-chloro-3-nitrobenzophenone;4-hydroxy-4′-chlorobenzophenone; 2,4-dihydroxybenzophenone;2,4-dimethylbenzophenone; 2,5-dimethylbenzophenone;3,4-diaminobenzophenone; 3,4-dichlorobenzophenone;3,4-difluorobenzophenone; 3,4-dihydroxybenzophenone;3,4-dimethylbenzophenone; 4,4′-bis(diethylamine)benzophenone;4,4′-bis(dimethylamine)benzophenone; 4,4′-dichlorobenzophenone;4,4′-difluorobenzophenone; 4,4′-dihydroxybenzophenone; and4,4′-dimethoxybenzophenone.

In another embodiment, the stabilizers of the present invention compriseat least one aryl sulfide. The aryl sulfide stabilizers comprise atleast one selected from the group consisting of benzyl phenyl sulfide,diphenyl sulfide, and dibenzyl sulfide.

In another embodiment, the stabilizers of the present invention compriseat least one terephthalate. The terephthalate stabilizers includedivinyl terephthalate (CAS reg. no. [13486-19-0]) and diphenylterephthalate (CAS reg. no. [1539-04-4]).

In one embodiment, the compositions of the present invention furthercomprising at least one additional stabilizer compound selected from thegroup consisting of phenols, phosphites, terpenes, terpenoids, andmixtures thereof.

In another embodiment, the additional stabilizer may comprise at leastone phenol. Phenol stabilizers comprise any substituted or unsubstitutedphenol compound including phenols comprising one or more substituted orunsubstituted cyclic, straight chain, or branched aliphatic substituentgroup, such as, alkylated monophenols including2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol;2,4-dimethyl-6-tertbutylphenol; tocopherol; and the like, hydroquinoneand alkylated hydroquinones including t-butyl hydroquinone, otherderivatives of hydroquinone; and the like, hydroxylated thiodiphenylethers, including 4,4′-thio-bis(2-methyl-6-tert-butylphenol);4,4′-thiobis(3-methyl-6-tertbutylphenol);2,2′-thiobis(4methyl-6-tert-butylphenol); and the like,alkylidene-bisphenols including:4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-bis(2,6-di-tert-butylphenol); derivatives of 2,2′- or4,4-biphenoldiols; 2,2′-methylenebis(4-ethyl-6-tertbutylphenol);2,2′-methylenebis(4-methyl-6-tertbutylphenol);4,4-butylidenebis(3-methyl-6-tert-butylphenol);4,4-isopropylidenebis(2,6-di-tert-butylphenol);2,2′-methylenebis(4-methyl-6-nonylphenol);2,2′-isobutylidenebis(4,6-dimethylphenol;2,2′-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4-biphenyldiolsincluding 2,2′-methylenebis(4-ethyl-6-tert-butylphenol);butylatedhydroxy toluene (BHT), bisphenols comprising heteroatomsincluding 2,6-di-tert-alpha-dimethylamino-p-cresol,4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols;2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol); sulfides including;bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; and mixtures thereof,meaning mixtures of any of the phenol stabilizers listed in thisparagraph.

In another embodiment, the additional stabilizer may comprise at leastone phosphite. Phosphite stabilizers may be derived from substitutedphosphites, including hindered phosphites. In particular, hinderedphosphites are derivatives of alkyl, aryl or alkylaryl phosphitecompounds. The hindered phosphites include tris-(di-tert-butylphenyl)phosphite, di-n-octyl phosphite, and iso-decyl diphenyl phosphate.Tris-(di-tert-butylphenyl) phosphite is sold under the trademarkIrgafos® 168, di-n-octyl phosphite is sold under the trademark Irgafos®OPH, and iso-decyl diphenyl phosphite) is sold under the trademarkIrgafos® DDPP, all by Ciba.

In another embodiment, the additional stabilizer may comprise at leastone terpene. Terpenes comprise hydrocarbon compounds characterized bystructures containing more than one repeating isoprene(2-methyl-1,3-butadiene) unit. Representative terpenes include but arenot limited to myrcene (2-methyl-6-methyl-eneocta-1,7-diene),allo-ocimene, beta-ocimene, terebene, limonene (in particulard-limonene), retinal, pinene, menthol, geraniol, famesol, phytol,Vitamin A, terpinene, delta-3-carene, terpinolene, phellandrene,fenchene, dipentene, and mixtures thereof, meaning mixtures of any ofthe terpene stabilizers listed in this paragraph. Terpene stabilizersare commercially available or may be prepared by methods known in theart or isolated from natural sources.

In another embodiment, the additional stabilizer may comprise at leastone terpenoid. Terpenoids comprise natural products and relatedcompounds characterized by structures containing more than one repeatingisoprene unit and usually contain oxygen. Representative terpenoidsinclude carotenoids, such as lycopene (CAS reg. no. [502-65-8]), betacarotene (CAS reg. no. [7235-40-7]), and xanthophylls, i.e. zeaxanthin(CAS reg. no. [144-68-3]); retinoids, such as hepaxanthin (CAS reg. no.[512-39-0]), and isotretinoin (CAS reg. no. [4759-48-2]); abietane (CASreg. no. [640-43-7]); ambrosane (CAS reg. no. [24749-18-6]); aristolane(CAS reg. no. [29788-49-6]); atisane (CAS reg. no. [24379-83-7]);beyerane (CAS reg. no. [2359-83-3]), bisabolane (CAS reg. no.[29799-19-7]); bomane (CAS reg. no. [464-15-3]); caryophyllane (CAS reg.no. [20479-00-9]); cedrane (CAS reg. no. [13567-54-9]); dammarane (CASreg. no. [545-22-2]); drimane (CAS reg. no. [5951-58-6]); eremophilane(CAS reg. no. [3242-05-5]); eudesmane (CAS reg. no. [473-11-0]);fenchane (CAS reg. no. [6248-88-0]); germacrane (CAS reg. no.[559-65-9]); germacrane (CAS reg. no. [645-10-3]); gibbane (CAS reg. no.[6902-95-0]); grayanotoxane (CAS reg. no. [39907-73-8]); guaiane (CASreg. no. [489-80-5]); himachalane (CAS reg. no. [20479-45-2]); hopane(CAS reg. no. [471-62-5]); humulane (CAS reg. no. [430-19-3]); kaurane(CAS reg. no. [1573-40-6]); labdane (CAS reg. no. [561-90-0]); lanostane(CAS reg. no. [474-20-4]); lupane (CAS reg. no. [464-99-3]); p-menthane(CAS reg. no. [99-82-1]); oleanane (CAS reg. no. [471-67-0]);ophiobolane (CAS reg. no. [20098-65-1]); picrasane (CAS reg. no.[35732-97-9]); pimarane (CAS reg. no. [30257-03-5]); pinane (CAS reg.no. [473-55-2]); podocarpane (CAS reg. no. [471-78-3]); protostane (CASreg. no. [70050-78-1]); rosane (CAS reg. no. [6812-82-4]); taxane (CASreg. no. [1605-68-1]); thujane (CAS reg. no. [471-12-5]); trichothecane(CAS reg. no. [24706-08-9]), ursane (CAS reg. no. [464-93-7]), andmixtures thereof, meaning mixtures of any of the terpenoids listed inthis paragraphs. The terpenoids of the present invention arecommercially available or may be prepared by methods known in the art ormay be isolated from the naturally occurring source.

Unless otherwise noted above, the stabilizers of the present inventionare commercially available from various chemical supply houses.

Single stabilizer compounds may be used in combination in the presentcompositions comprising at least one fluoroolefin or multiple stabilizercompounds may be combined in any proportion to serve as a stabilizerblend. The stabilizer blend may contain multiple stabilizer compoundsfrom the same class of compounds or multiple stabilizer compounds fromdifferent classes of compounds. For example, a stabilizer blend maycontain 2 or more thiophosphates, or one or more thiophosphate incombination with one or more lactones.

Additionally, some of the stabilizer compounds exist as multipleconfigurational isomers or stereoisomers. Single isomers or multipleisomers of the same compound may be used in any proportion to preparethe stabilizer blend. Further, single or multiple isomers of a givencompound may be combined in any proportion with any number of othercompounds to serve as a stabilizer blend. The present invention isintended to include all single configurational isomers, singlestereoisomers or any combination or mixture thereof.

The present invention further provides a composition comprising at leastone fluoroolefin selected from the group consisting of HFC-1225ye,HFC-1234yf, HFC-1234ze and HFC-1243zf, and an effective amount of astabilizer comprising at least one epoxide, fluorinated expoxide ormixtures thereof.

Of particular note are stabilizer compositions comprising combinationsof compounds that provide an unexpected level of stabilization. Certainof these combinations may serve as synergistic stabilizer compositions,that is, the compositions of compounds that augment each others'efficiency in a formulation and the stabilization obtained is largerthan that expected from the sum of the contributions of the individualcomponents. Such synergistic stabilizer compositions may comprise atleast one phosphorus-containing compound and any of the additionalcompounds selected from the group consisting of terpenes and terpenoids,fullerenes, epoxides, fluorinated epoxides, oxetanes,divinylterephthalate, and diphenylterephthalate, and mixtures thereof,meaning mixtures of any of the foregoing additional compounds with aphosphorus-containing compound.

A limiting factor in the effectiveness of a stabilizer composition isthe consumption of stabilizer and loss of functionality over the time ofactive use. Of particular note are synergistic stabilizer compositionscomprising mixtures of stabilizers that include components capable ofregenerating the consumed stabilizer during active use, hereinafterreferred to as regenerative stabilizers. Unlike multi-functional single,large stabilizer compounds comprising multiple stabilizing functionalgroups, regenerative stabilizers comprising small “synergistic”stabilizers function with higher mobility and higher stabilization rates(meaning higher rates of reaction by which the stabilization isoccurring). Regenerative stabilizer composition contains one or morestabilizers that can replenish itself or themselves after use, so thatover long-term use, the composition's efficacy is maintained.

An example of a regenerative stabilizer is at least one epoxide orfluorinated epoxide and at least one amine. Amines for inclusion in theregenerative stabilizer compositions may comprise any of the hinderedamine antioxidants as described previously herein. Of particular note,are those hindered amines derived from substituted piperidine compounds,in particular derivatives of an alkyl-substituted piperidyl,piperidinyl, piperazinone, or alkoxypiperidinyl compounds, and mixturesthereof. Representative hindered amine antioxidants are2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol;bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate (CAS reg. no.[41556-26-7]); di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, such as thehindered amine commercially available under the trademark Tinuvin® 770by Ciba; poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidylsuccinate (CAS reg. no. [65447-77-0]), such as that commerciallyavailable under the trademark Tinuvin® 622LD from Ciba; alkylatedparaphenylenediamines, such asN-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine, orN,N′-di-sec-butyl-p-phenylenediamine; and hydroxylamines such as tallowamines or N-methylbis(hydrogenated tallow alkyl)amine. Some otherhindered amine antioxidants include the amine antioxidant commerciallyavailable from Ciba under the trademark Tinuvin® 765, or commerciallyavailable from Mayzo, Inc. under the trademark BLS® 1944 and BLS® 1770.The amines also include mixtures of any of the amines listed in thisparagraph.

Another example of regenerative stabilizer is a stabilizer whichcomprises at least one epoxide or fluorinated epoxide, combined with atleast one phosphite. Of particular note are phosphites, which can bederived from substituted phosphites in particular, derivatives of alky,aryl phosphite compounds. Representative phosphites which can be usedfor regenerative stabilizers include (tris-(di-tert-butylphenyl)phosphite), sold under the trademark Irgafos® 168, (di-n-octylphosphite), sold under the trademark Irgafos® OPH and (Iso-decyldiphenyl phosphite), sold under the trademark Irgafos® DDPP (all fromCiba).

In another embodiment, any stabilizer composition as described aboveherein may further comprise at least one metal deactivator selected fromthe group consisting of areoxalyl bis(benzylidene)hydrazide (CAS reg.no. 6629-10-3);N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine) (CAS reg.no. 32687-78-8);2,2′-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate) (CASreg. no. 70331-94-1); N,N′-(disalicyclidene)-1,2-propanediamine (CASreg. no. 94-91-1); ethyenediaminetetraacetic acid (CAS reg. no. 60-00-4)and salts thereof; triazoles; benzotriazole, 2-mercaptobenzothiazole,tolutriazole derivatives, N,N-disalicylidene-1,2-diaminopropane, andmixtures thereof.

In another embodiment, the present disclosure provides a compositioncomprising a. at least one fluoroolefin; and b. an effective amount of astabilizer comprising i) at least one epoxide, fluorinated epoxide ormixture thereof; ii) at least one phosphite, phenol, terpene, terpenoid,or mixture thereof; and iii) at least one metal deactivator selectedfrom the group consisting of areoxalyl bis(benzylidene)hydrazide;N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine);2,2′-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate);N,N′-(disalicyclidene)-1,2-propanediamine; ethyenediaminetetraaceticacid and salts thereof; triazoles; benzotriazole,2-mercaptobenzothiazole, tolutriazole derivatives,N,N-disalicylidene-1,2-diaminopropane, and mixtures thereof. Phosphitessuitable for inclusion in the above mentioned compositions may behindered phosphites derived from substituted phosphites. In particular,hindered phosphites are derivatives of alkyl, aryl or alkylarylphosphite compounds. Representative hindered phosphites are Irgafos 168(Tris-(di-tert-butylphenyl) phosphite), Irgafos OPH (Di-n-octylphosphite), and Irgafos DDPP (Iso-decyl diphenyl phosphite) (all fromCiba). Phenols suitable for inclusion in the above mentionedcompositions may be any substituted or unsubstituted phenol compoundincluding phenols comprising one or more substituted or unsubstitutedcyclic, straight chain, or branched aliphatic substituent group, suchas, alkylated monophenols including 2,6-di-tert-butyl-4-methylphenol;2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tertbutylphenol;tocopherol; and the like, hydroquinone and alkylated hydroquinonesincluding t-butyl hydroquinone, other derivatives of hydroquinone; andthe like, hydroxylated thiodiphenyl ethers, including4,4′-thio-bis(2-methyl-6-tert-butylphenol);4,4′-thiobis(3-methyl-6-tertbutylphenol);2,2′-thiobis(4-methyl-6-tert-butylphenol); and the like,alkylidene-bisphenols including:4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-bis(2,6-di-tert-butylphenol); derivatives of 2,2′- or4,4-biphenoldiols; 2,2′-methylenebis(4-ethyl-6-tertbutylphenol);2,2′-methylenebis(4-methyl-6-tert-butylphenol);4,4-butylidenebis(3-methyl-6-tert-butylphenol);4,4-isopropylidenebis(2,6-di-tert-butylphenol);2,2′-methylenbis(4-methyl-6-nonylphenol);2,2′-isobutylidenebis(4,6-dimethylphenol;2,2′-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4-biphenyldiolsincluding 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); butylatedhydroxyl toluene (BHT), bisphenols comprising heteroatoms including2,6-di-tert-alpha-dimethylamino-p-cresol,4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols;2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol); sulfides including;bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; and the like. Terpenessuitable for inclusion in the above mentioned compositions arehydrocarbon compounds characterized by structures containing one or morerepeating isoprene (2-methyl-1,3-butadiene) unit. Terpenes may beacyclic or cyclic. Representative terpenes include but are not limitedto isoprene, myrcene (2-methyl-6-methyl-eneocta-1,7-diene), allo-cimene,beta-ocimene, terebene, limonene (in particular d-limonene), retinal,pinene, menthol, geraniol, famesol, phytol, Vitamin A, terpinene,delta-3-carene, terpinolene, phellandrene, fenchene, dipentene, andmixtures thereof. Terpene stabilizers are commercially available or maybe prepared by methods known in the art or isolated from naturalsources. Terpenoids suitable for inclusion in the above mentionedcompositions are natural products and related compounds characterized bystructures containing more than one repeating isoprene unit and usuallycontain oxygen. Representative terpenoids include carotenoids, such aslycopene (CAS reg. no. [502-65-8]), betacarotene (CAS reg. no.[7235-40-7]), and xanthophylls, i.e. zeaxanthin (CAS reg. no.[144-68-3]); retinoids, such as hepaxanthin (CAS reg. no. [512-39-0]),and isotretinoin (CAS reg. no. [4759-48-2]); abietane (CAS reg. no.[640-43-7]); ambrosane (CAS reg. no. [24749-18-6]); aristolane (CAS reg.no. [29788-49-6]); atisane (CAS reg. no. [24379-83-7]); beyerane (CASreg. no. [2359-83-3]), bisabolane (CAS reg. no. [29799-19-7]); bomane(CAS reg. no. [464-15-3]); caryophyllane (CAS reg. no. [20479-00-9]);cedrane (CAS reg. no. [13567-54-9]); dammarane (CAS reg. no.[545-22-2]); drimane (CAS reg. no. [5951-58-6]); eremophilane (CAS reg.no. [3242-05-5]); eudesmane (CAS reg. no. [473-11-0]); fenchane (CASreg. no. [6248-88-0]); gammacerane (CAS reg. no. [559-65-9]); germacrane(CAS reg. no. [645-10-3]); gibbane (CAS reg. no. [6902-95-0]);grayanotoxane (CAS reg. no. [39907-73-8]); guaiane (CAS reg. no.[489-80-5]); himachalane (CAS reg. no. [20479-45-2]); hopane (CAS reg.no. [471-62-5]); humulane (CAS reg. no. [430-19-3]); kaurane (CAS reg.no. [1573-40-6]); labdane (CAS reg. no. [561-90-0]); lanostane (CAS reg.no. [474-20-4]); lupane (CAS reg. no. [464-99-3]); p-menthane (CAS reg.no. [99-82-1]); oleanane (CAS reg. no. [471-67-0]); ophiobolane (CASreg. no. [20098-65-1]); picrasane (CAS reg. no. [35732-97-9]); pimarane(CAS reg. no. [30257-03-5]); pinane (CAS reg. no. [473-55-2]);podocarpane (CAS reg. no. [471-78-3]); protostane (CAS reg. no.[70050-78-1]); rosane (CAS reg. no. [6812-82-4]); taxane (CAS reg. no.[1605-68-1]); thujane (CAS reg. no. [471-12-5]); trichothecane (CAS reg.no. [24706-08-9]); and ursane (CAS reg. no. [464-93-7]). The terpenoidsof the present invention may be prepared by methods known in the art ormay be isolated from the naturally occurring source.

The compositions of the present invention may further comprise at leastone additional compound selected from the group consisting offluoroolefins (as described previously herein), hydrofluorocarbons,hydrocarbons, dimethyl ether, CF₃I, carbon dioxide (CO₂), ammonia, andmixtures thereof.

In one embodiment, additional compounds comprise at least onehydrofluorocarbon (HFC) compound. Hydrofluorocarbons of the presentinvention comprise saturated compounds containing carbon, hydrogen, andfluorine. Of particular utility are hydrofluorocarbons having 1-7 carbonatoms and having a normal boiling point of from about −90° C. to about80° C. Hydrofluorocarbons are commercial products available from anumber of sources such as E. I. du Pont de Nemours & Co.,Fluoroproducts, Wilmington, DE, 19898, USA, or may be prepared bymethods known in the art. Representative hydrofluorocarbon compoundsinclude but are not limited to fluoromethane (CH₃F, HFC-41),difluoromethane (CH₂F2, HFC-32), trifluoromethane (CHF₃, HFC-23),pentafluoroethane (CF₃CHF₂, HFC-125), 1,1,2,2-tetrafluoroethane(CHF₂CHF₂, HFC-134), 1,1,1,2-tetrafluoroethane (CF₃CH₂F, HFC-134a),1,1,1-trifluoroethane (CF₃CH₃, HFC-143a), 1,1-difluoroethane (CHF₂CH₃,HFC-152a), fluoroethane (CH₃CH₂F, HFC-161),1,1,1,2,2,3,3-heptafluoropropane (CF₃CF₂CHF₂, HFC-227ca),1,1,1,2,3,3,3-heptafluoropropane (CF₃CHFCF₃, HFC-227ea),1,1,2,2,3,3,-hexafluoropropane (CHF₂CF₂CHF₂, HFC-236ca),1,1,1,2,2,3-hexafluoropropane (CF₃CF₃CH₂F, HFC-236cb),1,1,1,2,3,3-hexafluoropropane (CF₃CHFCHF₂, HFC-236ea),1,1,1,3,3,3-hexafluoropropane (CF₃CH₂CF₃, HFC-236fa),1,1,2,2,3-pentafluoropropane (CHF₂CF₂CH₂F, HFC-245ca),1,1,1,2,2-pentafluoropropane (CF₃CF₂CH₃, HFC-245cb),1,1,2,3,3-pentafluoropropane (CHF₂CHFCHF₂, HFC-245ea),1,1,1,2,3-pentafluoropropane (CF₃CHFCH₂F, HFC-245eb),1,1,1,3,3-pentafluoropropane (CF₃CH₂CHF₂, HFC-245fa),1,2,2,3-tetrafluoropropane (CH₂FCF₂CH₂F, HFC-254ca),1,1,2,2-tetrafluoropropane (CHF₂CF₂CH₃, HFC-254cb),1,1,2,3-tetrafluoropropane (CHF₂CHFCH₂F, HFC-254ea),1,1,1,2-tetrafluoropropane (CF₃CHFCH₃, HFC-254eb),1,1,3,3-tetrafluoropropane (CHF₂CH₂CHF₂, HFC-254fa),1,1,1,3-tetrafluoropropane (CF₃CH₂CH₂F, HFC-254fb),1,1,1-trifluoropropane (CF₃CH₂CH₃, HFC-263fb), 2,2-difluoropropane(CH₃CF₂CH₃, HFC-272ca), 1,2-difluoropropane (CH₂FCHFCH₃, HFC-272ea),1,3-difluoropropane (CH₂FCH₂CH₂F, HFC-272fa), 1,1-difluoropropane(CHF₂CH₂CH₃, HFC-272fb), 2-fluoropropane (CH₃CHFCH₃, HFC-281ea),1-fluoropropane (CH₂FCH₂CH₃, HFC-281fa),1,1,2,2,3,3,4,4-octafluorobutane (CHF₂CF₂CF₂CHF₂, HFC-338pcc),1,1,1,2,2,4,4,4-octafluorobutane (CF₃CH₂CF₂CF₃, HFC-338mf),1,1,1,3,3-pentafluorobutane (CF₃CH₂CHF₂, HFC-365mfc),1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF₃CHFCHFCF₂CF₃, HFC-43-10mee),and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane(CF₃CF₂CHFCHFCF₂CF₂CF₃, HFC-63-14mee).

In another embodiment, additional compounds comprise at least onehydrocarbon. The hydrocarbons of the present invention comprisecompounds having only carbon and hydrogen. Of particular utility arecompounds having 3-7 carbon atoms. Hydrocarbons are commerciallyavailable through numerous chemical suppliers. Representativehydrocarbons include but are not limited to propane, n-butane,isobutane, cyclobutane, n-pentane, 2-methylbutane, 2,2-dimethylpropane,cyclopentane, n-hexane, 2-methylpentane, 2,2-dimethylbutane,2,3-dimethylbutane, 3-methylpentane, cyclohexane, n-heptane, andcycloheptane.

In another embodiment, additional compounds may also comprisehydrocarbons containing heteroatoms, such as dimethylether (DME,CH₃OCH₃. DME is commercially available.

In another embodiment, additional compounds may also compriseiodotrifluoromethane (CF₃I), which is commercially available fromvarious sources or may be prepared by methods known in the art.

In another embodiment, additional compounds may also comprise carbondioxide (CO₂), which is commercially available from various sources ormay be prepared by methods known in the art.

In another embodiment, additional compounds may also comprise ammonia(NH₃), which is commercially available from various sources or may beprepared by methods known in the art.

In another embodiment, of particular note are additional compoundsincluding compositions comprising: HFC-1225ye and HFC-32; HFC-1225ye andHFC-134a; HFC-1225ye, HFC-134a, and HFC-32; HFC-1225ye and HFC-1234yf;HFC-1225ye, HFC-1234yf, and HFC-32; and HFC-1225ye, HFC-1234yf andHFC-125.

In another embodiment, additional compounds include compositionscomprising fluoroolefins as disclosed in U.S. patent application Ser.No. 11/369,227 filed Mar. 2, 2006; U.S. patent application Ser. No.11/393,109 filed Mar. 30, 2006; and U.S. patent application Ser. No.11/486,791 filed Jul. 13, 2006; are intended to be included within thescope of the present invention.

The compositions of the present invention may further comprise at leastone lubricant. Lubricants of the present invention comprise thosesuitable for use with refrigeration or air-conditioning apparatus. Amongthese lubricants are those conventionally used in compressionrefrigeration apparatus utilizing chlorofluorocarbon refrigerants. Suchlubricants and their properties are discussed in the 1990 ASHRAEHandbook, Refrigeration Systems and Applications, chapter 8, titled“Lubricants in Refrigeration Systems”, pages 8.1 through 8.21, hereinincorporated by reference. Lubricants of the present invention maycomprise those commonly known as “mineral oils” in the field ofcompression refrigeration lubrication. Mineral oils comprise paraffins(i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons),naphthenes (i.e. cyclic or ring structure saturated hydrocarbons, whichmay be paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbonscontaining one or more rings characterized by alternating double bonds).Lubricants of the present invention further comprise those commonlyknown as “synthetic oils” in the field of compression refrigerationlubrication. Synthetic oils comprise alkylaryls (i.e. linear andbranched alkyl alkylbenzenes), synthetic paraffins and naphthenes,silicones, and polyalphaolefins. Representative conventional lubricantsof the present invention are the commercially available BVM 100 N(paraffinic mineral oil sold by BVA Oils), napthenic mineral oilcommercially available under the trademark from Suniso® 3GS and Suniso®5GS by Crompton Co., naphthenic mineral oil commercially available fromPennzoil under the trademark Sontex® 372LT, naphthenic mineral oilcommercially available from Calumet Lubricants under the trademarkCalumet RO-30, linear alkylbenzenes commercially available from ShrieveChemicals under the trademarks Zerol® 75, Zerol® 150 and Zerol® 500 andbranched alkylbenzene, sold by Nippon Oil as HAB 22.

Lubricants of the present invention further comprise those which havebeen designed for use with hydrofluorocarbon refrigerants and aremiscible with refrigerants of the present invention under compressionrefrigeration and air-conditioning apparatus' operating conditions. Suchlubricants and their properties are discussed in “Synthetic Lubricantsand High-Performance Fluids”, R. L. Shubkin, editor, Marcel Dekker,1993. Such lubricants include, but are not limited to, polyol esters(POEs) such as Castrol 100 (Castrol, United Kingdom), polyalkyleneglycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland,Michigan), and polyvinyl ethers (PVEs).

Lubricants of the present invention are selected by considering a givencompressor's requirements and the environment to which the lubricantwill be exposed.

The compositions of the present invention that may be prepared by anyconvenient method to combine the desired amount of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combine the components in an appropriate vessel.Agitation may be used, if desired.

Any suitable effective amount of stabilizer may be used in thecompositions comprising at least one fluoroolefin. As described herein,the phrase “effective amount” refers to an amount of stabilizer of thepresent invention which, when added to a composition comprising at leastone fluoroolefin, results in a composition that will not degrade toproduce as great a reduction in refrigeration performance when in use ina cooling apparatus as compared to the composition without stabilizer.Such effective amounts of stabilizer may be determined by way of testingunder the conditions of standard test ASHRAE 97-2004. In a certainembodiment of the present invention, an effective amount may be said tobe that amount of stabilizer that when combined with a compositioncomprising at least one fluoroolefin allows a cooling apparatusutilizing said composition comprising at least one fluoroolefin toperform at the same level of refrigeration performance and coolingcapacity as if a composition comprising 1,1,1,2-tetrafluoroethane(R-134a), or other standard refrigerant (R12, R22, R502, R507A, R508,R401A, R401B, R402A, R402B, R408, R41OA, R404A, R407C, R413A, R417A,R422A, R422B, R422C, R422D, R423, R114, R11, R113, R123, R124, R236fa,or R245fa) depending upon what refrigerant may have been used in asimilar system in the past, were being utilized as the working fluid.

Certain embodiments include effective amounts of stabilizer for use inthe present invention that comprise from about 0.001 weight percent toabout 10 weight percent, more preferably from about 0.01 weight percentto about 5 weight percent, even more preferably from about 0.3 weightpercent to about 4 weight percent and even more preferably from about0.3 weight percent to about 1 weight percent based on the total weightof compositions comprising at least one fluoroolefin as describedherein.

The present invention further relates to a method for stabilizing acomposition comprising at least one fluoroolefin, said method comprisingadding an effective amount of a stabilizer comprising: a. at least oneepoxide or fluorinated epoxide; and b. at least one compound selectedfrom the group consisting of thiophosphates, butylatedtriphenylphosphorothionates, organophosphates, fullerenes,functionalized perfluoropolyethers, polyoxyalkylated aromatics,alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalate, diphenylterephthalate, and mixtures thereof.

The present invention further relates to a process for producing coolingcomprising condensing a composition comprising at least one fluoroolefinand an effective amount of a stabilizer comprising: a. at least oneepoxide or fluorinated epoxide; and b. at least one compound selectedfrom the group consisting of thiophosphates, butylatedtriphenylphosphorothionates, organophosphates, fullerenes,functionalized perfluoropolyethers, polyoxyalkylated aromatics,alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalate, diphenylterephthalate, and mixtures thereof, and thereafter evaporating saidcomposition in the vicinity of a body to be cooled.

A body to be cooled may be any space, location or object requiringrefrigeration or air-conditioning. In stationary applications the bodymay be the interior of a structure, i.e. residential or commercial, or astorage location for perishables, such as food or pharmaceuticals. Formobile refrigeration applications the body may be incorporated into atransportation unit for the road, rail, sea or air. Certainrefrigeration systems operate independently with regards to any movingcarrier, these are known as “intermodal” systems. Such intermodalsystems include “containers” (combined seal and transport) as well as“swap bodies” (combined road and rail transport).

The present invention further relates to a process for producing heatcomprising condensing a composition comprising at least one fluoroolefinand an effective amount of a stabilizer comprising: a. at least oneepoxide or fluorinated epoxide; and b. at least one compound selectedfrom the group consisting of thiophosphates, butylatedtriphenylphosphorothionates, organophosphates, fullerenes,functionalized perfluoropolyethers, polyoxyalkylated aromatics,alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalate, diphenylterephthalate, and mixtures thereof in the vicinity of a body to beheated, and thereafter evaporating said composition.

A body to be heated may be any space, location or object requiring heat.These may be the interior of structures either residential or commercialin a similar manner to the body to be cooled. Additionally, mobile unitsas described for cooling may be similar to those requiring heating.Certain transport units require heating to prevent the material beingtransported from solidifying inside the transport container.

It is not uncommon for air to leak into a refrigeration,air-conditioning system or heat pump. The oxygen in the air may lead tooxidation of certain components of the system including the workingfluid. Thus, in another embodiment, also disclosed is a method forreducing degradation of a composition comprising at least onefluoroolefin, wherein said degradation is caused by the presence ofinadvertent air; for example in a refrigeration, air-conditioning orheat pump system, said method comprising adding an effective amount of astabilizer comprising at least one epoxide or fluorinated epoxide and atleast one compound selected from the group consisting of thiophosphates,butylated triphenylphosphorothionates, organo phosphates, fullerenes,functionalized perfluoropolyethers, polyoxyalkylated aromatics,alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalate, diphenylterephthalate, and mixtures thereof to the composition comprising atleast one fluoroolefin.

In another embodiment, also disclosed is a method for reducing reactionwith oxygen for a composition comprising at least one fluoroolefins,said method comprising adding an effective amount of a stabilizercomprising at least one epoxide or fluorinated epoxide and at least onecompound selected from the group consisting of thiophosphates, butylatedtriphenylphosphorothionates, organo phosphates, fullerenes,functionalized perfluoropolyethers, polyoxyalkylated aromatics,alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,thioethers, amines, nitromethane, alkylsilanes, benzophenonederivatives, aryl sulfides, divinyl terephthalate, diphenylterephthalate, and mixtures thereof to the composition comprising atleast one fluoroolefin.

EXAMPLE Refrigeration System Chemical Stability

A chemical stability test is run under conditions described in ASHRAE(American Society of Heating, Refrigerating and Air-ConditioningEngineers) Standard 97-2004 to determine chemical stability of thestabilized compositions of the present invention as compared tocompositions with no stabilizers.

The procedure is given here:

-   -   1. Metal coupons of copper, aluminum and steel are placed in        thick walled glass tubes.    -   2. Working fluid samples, including lubricant, are prepared with        and without stabilizers, and optionally with 2 volume % air        added to the tube.    -   3. Samples are added to the glass tubes as described in the        standard.    -   4. The tubes are sealed with a glass blowing torch.    -   5. The sealed tubes are heated in an oven for 14 days at the        specified temperature.    -   6. After 14 days, the sealed tubes are removed from the oven and        examined for metal/liquid appearance, proper volume of liquid,        appearance of glass, and absence of extraneous materials such as        metal fines.    -   7. Ratings are assigned to each sample based upon the following        criteria (per industry practice):        -   1=light changes on coupons and liquids;        -   2=light to moderate changes on coupons or liquids;        -   3=moderate to significant changes on coupons or liquids;        -   4=severe changes on coupons or liquids;        -   5=extreme changes on coupons or liquids, i.e. black liquid            or coked with many deposits.            Table 4 lists estimated results for stabilizers of the            present invention as compared to unstabilized compositions.            Ucon® PAG 488 is a trademark for a polyalkylene glycol            lubricant commercially available from The Dow Chemical            Company. Irgalube® 63 is a trademark for a dithiophosphate            commercially available from Ciba. Irgalube® 232 is a            trademark for a butylated triphenyl phosphorothionate            commercially available from Ciba. Irgalube® 349 is a            trademark for a mixture of amine phosphates (an example of            an organophosphate) commercially available from Ciba.            Irgalube® 350 and Irgalube® 353 are trademarks for dialkyl            dithiophosphate esters from Ciba. Krytox® 157FSL is a            trademark for a functionalized perfluoropolyether            commercially available from DuPont. Zerol® 150 is a            trademark for an alkyl benzene lubricant sold by Shrieve            Chemical. OXT-101 is 3-ethyl-3-hydroxymethyloxetane from            Toagosei Company. Tinuvin® 622LD is a trademark for a            hindered amine antioxidant commercially available from Ciba.            HP-136 is            5,7-di-t-butyl-3-(3-4-dimethylphenyl)-3H-benzofuran-2-one            (an example of a lactone) from Ciba. The lubricant Ucon® PAG            488 is combined with the working fluid as set forth in Table            4 below to produce a composition that was 50 wt % working            fluid and 50 wt % lubricant.

TABLE 4 Stabilizer (wt % in With refrig/ 2 lubricant vol % Temp Workingfluid Lubricant Stabilizer mixture) Air (° C.) Rating HFC-1225ye PAG 488None 0 yes 175 4 HFC-1225ye PAG 488 None 0 no 175 2 HFC-1225ye PAG 488Irgalube ® 63 2 yes 175 2 HFC-1225ye PAG 488 Irgalube ® 63 2 no 175 1HFC-1225ye PAG 488 Irgalube ® 232 2 yes 175 2 HFC-1225ye PAG 488Irgalube ® 232 2 no 175 1 HFC-1225ye PAG 488 Irgalube ® 349 2 yes 175 2HFC-1225ye PAG 488 Irgalube ® 349 2 no 175 1 HFC-1225ye PAG 488Irgalube ® 350 2 yes 175 2 HFC-1225ye PAG 488 Irgalube ® 350 2 no 175 1HFC-1225ye PAG 488 Irgalube ® 353 2 yes 175 2 HFC-1225ye PAG 488Irgalube ® 353 2 no 175 1 HFC-1225ye PAG 488 d-limonene 2 yes 175 2HFC-1225ye PAG 488 d-limonene 2 no 175 1 HFC-1225ye PAG 488buckminsterfullerene 2 yes 175 2 HFC-1225ye PAG 488 buckminsterfullerene2 no 175 1 HFC-1225ye PAG 488 graphite powder 2 yes 175 2 HFC-1225ye PAG488 graphite powder 2 no 175 1 HFC-1225ye PAG 488 naphthalene 2 yes 1752 HFC-1225ye PAG 488 naphthalene 2 no 175 1 HFC-1225ye PAG 488 Anisole 2yes 175 2 HFC-1225ye PAG 488 Anisole 2 no 175 1 HFC-1225ye PAG 488Krytox ® 157FSL 2 yes 175 2 HFC-1225ye PAG 488 Krytox ® 157FSL 2 no 1751 HFC-1225ye PAG 488 Zerol ® 150 2 yes 175 2 HFC-1225ye PAG 488 Zerol ®150 2 no 175 1 HFC-1225ye PAG 488 Trifluormethyloxirane 2 yes 175 2HFC-1225ye PAG 488 Trifluormethyloxirane 2 no 175 1 HFC-1225ye PAG 488OXT-101 2 yes 175 2 HFC-1225ye PAG 488 OXT-101 2 no 175 1 HFC-1225ye PAG488 ascorbic acid 2 yes 175 2 HFC-1225ye PAG 488 ascorbic acid 2 no 1751 HFC-1225ye PAG 488 methyl mercaptan 2 yes 175 2 HFC-1225ye PAG 488methyl mercaptan 2 no 175 1 HFC-1225ye PAG 488 gamma-undecalactone 2 yes175 2 HFC-1225ye PAG 488 gamma-undecalactone 2 no 175 1 HFC-1225ye PAG488 benzyl phenyl sulfide 2 yes 175 2 HFC-1225ye PAG 488 benzyl phenylsulfide 2 no 175 1 HFC-1225ye PAG 488 1,2-butylene oxide 2 yes 175 2HFC-1225ye PAG 488 1,2-butylene oxide 2 no 175 1 HFC-1225ye PAG 488diisopropylamine 2 yes 175 2 HFC-1225ye PAG 488 diisopropylamine 2 no175 1 HFC-1225ye PAG 488 nitromethane 2 yes 175 2 HFC-1225ye PAG 488nitromethane 2 no 175 1 HFC-1225ye PAG 488 tris(trimethylsilyl)silane 2yes 175 2 HFC-1225ye PAG 488 tris(trimethylsilyl)silane 2 no 175 1HFC-1225ye PAG 488 tocopherol 2 yes 175 2 HFC-1225ye PAG 488 tocopherol2 no 175 1 HFC-1225ye PAG 488 hydroquinone 2 yes 175 2 HFC-1225ye PAG488 hydroquinone 2 no 175 1 HFC-1225ye PAG 488 Butylated hydroxy 2 yes175 2 toluene (BHT) HFC-1225ye PAG 488 Butylated hydroxy 2 no 175 1toluene (BHT) HFC-1225ye PAG 488 Divinyl terephthalic acid 2 yes 175 2HFC-1225ye PAG 488 Divinyl terephthalic acid 2 no 175 1 HFC-1225ye PAG488 Tinuvin ® 622LD 2 yes 175 2 HFC-1225ye PAG 488 Tinuvin ® 622LD 2 no175 1 HFC-1225ye PAG 488 Mn(Cl)₂ with KCl 2 yes 175 2 HFC-1225ye PAG 488Mn(Cl)₂ with KCl 2 no 175 1 HFC-1225ye PAG 488 TiO₂ 2 yes 175 2HFC-1225ye PAG 488 TiO₂ 2 no 175 1 HFC-1225ye PAG 488 Na₂CO₃ 2 yes 175 2HFC-1225ye PAG 488 Na₂CO₃ 2 no 175 1 HFC-1225ye PAG 488 2-hydroxy-4- 2yes 175 2 methoxybenzophenone HFC-1225ye PAG 488 2-hydroxy-4- 2 no 175 1methoxybenzophenone HFC-1225ye PAG 488 2-hydroxybenzophenone 2 yes 175 2HFC-1225ye PAG 488 2-hydroxybenzophenone 2 no 175 1 HFC-1225ye PAG 4882,4-dihydroxybenzophenone 2 yes 175 2 HFC-1225ye PAG 4882,4-dihydroxybenzophenone 2 no 175 1 HFC-1225ye PAG 488 2,4- 2 yes 175 2dimethylbenzophenone HFC-1225ye PAG 488 2,4- 2 no 175 1dimethylbenzophenone HFC-1225ye PAG 488 3,4- 2 yes 175 2diaminobenzophenone HFC-1225ye PAG 488 3,4- 2 no 175 1diaminobenzophenone HFC-1225ye PAG 488 HP-136 2 yes 175 2 HFC-1225ye PAG488 HP-136 2 no 175 1Estimates indicate improved chemical stability in the presence ofstabilizers with and without air present.

What is claimed is:
 1. A composition consisting of at least onefluoroolefin and an effective amount of a stabilizer consisting of: a.at least one compound selected from the group consisting of an epoxideor a fluorinated epoxide represented by Formula A, wherein each of R²through R⁵ is H, alkyl of 1 to 6 carbon atoms, or fluoroalkyl of 1 to 6carbon atoms with the proviso that at least one of R² through R⁵ is afluoroalkyl group;

b. at least one compound selected from the group consisting oforganophosphates; and a hydrocarbon.
 2. The composition of claim 1,wherein the epoxide is selected from the group consisting of1,2-propylene oxide, 1,2-butylene oxide, butylphenylglycidyl ether,pentylphenylglycidyl ether, hexylphenylglycidyl ether,heptylphenylglycidyl ether, octylphenylglycidyl ether,nonylphenylglycidyl ether, decylphenylglycidyl ether, glycidylmethylphenylether, 1,4-glycidyl phenyl diether, 4-methoxyphenylglycidylether, naphthyl glycidyl ether, 1,4-diglycidyl naphthyl diether,butylphenyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidylether, hexanediol diglycidyl ether, allyl glycidyl ether, polypropyleneglycol diglycidyl ether, trifluoromethyloxirane,1,1-bis(trifluoromethyl)oxirane, and mixtures thereof.
 3. Thecomposition of claim 1, wherein the organophosphate is selected from thegroup consisting of amine phosphates, trialkyl phosphates, triarylphosphates, mixed alkyl-aryl phosphates, and cyclic phosphates.
 4. Thecomposition of claim 3, wherein the organophosphate is selected from thegroup consisting of trimethyl phosphate; triethyl phosphate; tributylphosphate; trioctyl phosphate; tri(2-ethylhexyl)phosphate; triphenylphosphate; tricresyl phosphate; trixylenyl phosphate; isopropylphenylphenyl phosphate; bis(t-butylphenyl) phenyl phosphate; butylatedtriphenyl phosphate; tert-butylated triphenyl phosphate; andiso-propylated triphenyl phosphate.
 5. The composition of claim 1wherein said fluoroolefin is at least one compound selected from thegroup consisting of: (i) fluoroolefins of the formula E- or Z—R′CH═CHR²,wherein R¹ and R² are, independently, C₁ to C₆ perfluoroalkyl groups;(ii) cyclic fluoroolefins of the formula cyclo-[CX═CY(CZW)_(n)—],wherein X, Y, Z, and W, independently, are H or F, and n is an integerfrom 2 to 5; and (iii) fluoroolefins selected from the group consistingof: 1,2,3,3,3-pentafluoro-1-propene (CHF═CFCF₃),1,1,3,3,3-pentafluoro-1-propene (CF₂═CHCF₃),1,1,2,3,3-pentafluoro-1-propene (CF₂═CFCHF₂),1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF₂),2,3,3,3-tetrafluoro-1-propene (CH₂═CFCF₃),1,3,3,3-tetrafluoro-1-propene, CHF═CHCF₃), 1,1,2,3-tetrafluoro-1-propene(CF₂═CFCH₂F), 1,1,3,3-tetrafluoro-1-propene (CF₂═CHCHF₂),1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF₂), 3,3,3-trifluoro-1-propene(CH₂═CHCF₃), 2,3,3-trifluoro-1-propene (CHF₂CF═CH₂);1,1,2-trifluoro-1-propene (CH₃CF═CF₂); 1,2,3-trifluoro-1-propene(CH₂FCF═CF₂); 1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);1,3,3-trifluoro-1-propene (CHF₂CH═CHF);1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF₃)₂C═CHF);1,1,3,3,4,4,4-heptafluoro-1-butene (CF₂═CHCF₂CF₃);1,1,2,3,4,4,4-heptafluoro-1-butene (CF₂═CFCHFCF₃);1,1,2,3,3,4,4-heptafluoro-1-butene (CF₂=CFCF₂CHF₂);2,3,3,4,4,4-hexafluoro-1-butene (CF₃CF₂CF═CH₂);1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF₂CF₃);1,2,3,4,4,4-hexafluoro-1-butene (CHF═CFCHFCF₃);1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF₂CHF₂);1,1,2,3,4,4-hexafluoro-2-butene (CHF₂CF═CFCHF₂);1,1,1,2,3,4-hexafluoro-2-butene (CH₂FCF═CFCF₃);1,1,1,2,4,4-hexafluoro-2-butene (CHF₂CH═CFCF₃);1,1,1,3,4,4-hexafluoro-2-butene (CF₃CH═CFCHF₂);1,1,2,3,3,4-hexafluoro-1-butene (CF₂═CFCF₂CH₂F);1,1,2,3,4,4-hexafluoro-1-butene (CF₂═CFCHFCRF2);3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);1,1,1,2,4-pentafluoro-2-butene (CH₂FCH═CFCF₃);1,1,1,3,4-pentafluoro-2-butene (CF₃CH═CFCH₂F);3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂);1,1,1,4,4-pentafluoro-2-butene (CHF₂CH═CHCF₃);1,1,1,2,3-pentafluoro-2-butene (CH₃CF═CFCF₃);2,3,3,4,4-pentafluoro-1-butene (CH₂═CFCF₂CHF₂);1,1,2,4,4-pentafluoro-2-butene (CHF₂CF═CHCHF₂);1,1,2,3,3-pentafluoro-1-butene (CH₃CF₂CF═CF₂);1,1,2,3,4-pentafluoro-2-butene (CH₂FCF═CFCHF₂);1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF₂═C(CF₃)(CH₃));2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH₂═C(CHF₂)(CF₃));2,3,4,4,4-pentafluoro-1-butene (CH₂═CFCHFCF₃);1,2,4,4,4-pentafluoro-1-butene (CHF═CFCH₂CF₃);1,3,4,4,4-pentafluoro-1-butene (CHF═CHCHFCF₃);1,3,3,4,4-pentafluoro-1-butene (CHF═CHCF₂CHF₂);1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF₂);3,3,4,4-tetrafluoro-1-butene (CH₂═CHCF₂CHF₂);1,1-difluoro-2-(difluoromethyl)-1-propene (CF₂═C(CHF₂)(CH₃));1,3,3,3-tetrafluoro-2-methyl-1-propene (CHF═C(CF₃)(CH₃));3,3-difluoro-2-(difluoromethyl)-1-propene (CH₂═C(CHF₂)₂);1,1,1,2-tetrafluoro-2-butene (CF₃CF═CHCH₃); 1,1,1,3-tetrafluoro-2-butene(CH₃CF═CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene(CF₃CF═CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene(CF₂═CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene(CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene(CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene(CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene(CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene(CF₂=CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene(CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene(CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene(CF₃CF═CFCHFCF₃); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene(CHF═CFCF(CF₃)₂); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene(CF₂═CFCH(CF₃)₂); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene(CF₃CH═C(CF₃)₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene(CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene(CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene(CHF═CFCF₂CF₂CHF₂); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene(CH₂═C(CF₃)CF₂CF₃); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene(CF₂═CHCH(CF₃)₂); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene(CHF═CHCF(CF₃)₂); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene(CF₂═C(CF₃)CH₂CF₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF₃CF₂CF₂CH═CH₂);2,3,3,4,4,5,5-heptafluoro-1-pentene (CH₂═CFCF₂CF₂CHF₂);1,1,3,3,5,5,5-heptafluoro-1-butene (CF₂═CHCF₂CH₂CF₃);1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF₃CF═C(CF₃)(CH₃));2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH₂═CFCH(CF₃)₂);1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCH(CF₃)₂);1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH₂FCH═C(CF₃)₂);1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH₃CF═C(CF₃)₂);1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF₃)₂C═CHCH₃);3,4,4,5,5,5-hexafluoro-2-pentene (CF₃CF₂CF═CHCH₃);1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF₃C(CH₃)═CHCF₃);3,3,4,5,5,5-hexafluoro-1-pentene (CH₂=CHCF₂CHFCF₃);4,4,4-trifluoro-2-(trifluoromethyl)-1-butene (CH₂═C(CF₃)CH₂CF₃);1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF₃(CF₂)₃CF═CF₂);1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF₃CF₂CF═CFCF₂CF₃);1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene((CF₃)₂C═C(CF₃)₂);1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene((CF₃)₂CFCF═CFCF₃);1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene((CF₃)₂C═CHC₂F₅);1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene(CF₃CF₂CF₂CF₂CH═CH₂); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene(CH₂═CHC(CF₃)₃);1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene((CF₃)₂C═C(CH₃)(CF₃));2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene(CH₂═CFCF₂CH(CF₃)₂); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene(CF₃CF═C(CH₃)CF₂CF₃);1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene (CF₃CH═CHCH(CF₃)₂);3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF₃CF₂CF₂CF═CHCH₃);3,3,4,4,5,5,6,6-octafluoro1-hexene (CH₂═CHCF₂CF₂CF₂CHF₂);1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF₃)₂C═CHCF₂CH₃);4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene (CH₂═C(CF₃)CH₂C₂F₅);3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF₃CF₂CF₂C(CH₃)═CH₂);4,4,5,5,6,6,6-heptafluoro-2-hexene (CF₃CF₂CF₂CH═CHCH₃);4,4,5,5,6,6,6-heptafluoro-1-hexene (CH₂═CHCH₂CF₂C₂F₅);1,1,1,2,2,3,4-heptafluoro-3-hexene (CF₃CF₂CF═CFC₂H₅);4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH₂═CHCH₂CF(CF₃)₂);1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF₃CF═CHCH(CF₃)(CH₃));1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene ((CF₃)₂C═CFC₂H₅);1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene(CF₃CF═CFCF₂CF₂C₂F₅);1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene(CF₃CF₂CF═CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene(CF₃CH═CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene(CF₃CF═CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene(CF₃CF₂CH═CFCF₂C₂F₅); and1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF₃CF₂CF═CHCF₂C₂F₅).6. The composition of claim 5, wherein the fluoroolefin is selected fromthe group consisting of 1,1,1,4,4,4-hexafluorobut-2-ene;1,1,1,4,4,5,5,5-octafluoropent-2-ene;1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene;1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene;1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene;1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene;1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene;1,1,1,4,5,5,6,6,6-nonafluoro-4-(trifluoromethyl)hex-2-ene;1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene;1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene;1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene;1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene;1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene;1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2-ene;1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene;1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene;1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept-3-ene;1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene;1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene;1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene;1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene;1,1,1,4,4,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-2-ene;1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-ene;1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene;1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene;1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-ene;1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3-ene;1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene;1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-ene;1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)oct-4-ene;1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene;1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3-ene;1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene;1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3-ene;1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-ene;1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene;1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene;1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)oct-3-ene;1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene;1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-ene;1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)oct-4-ene;1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene;1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-3-ene;1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene;1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec-5-ene;1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene;1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene;1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-bis(trifluoromethyl)oct-3-ene;1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-4-ene;1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)oct-4-ene;1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-ene;1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct-4-ene;1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-ene; and1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3-ene. 7.The compositions of claim 5, wherein the fluoroolefin is selected fromthe group consisting of 1,2,3,3,4,4-hexafluorocyclobutene;3,3,4,4-tetrafluorocyclobutene; 3,3,4,4,5,5,-hexafluorocyclopentene;1,2,3,3,4,4,5,5-octafluorocyclopentene; and1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene.
 8. A process for producingcooling comprising condensing the composition of claim 1 and thereafterevaporating said composition in the vicinity of a body to be cooled. 9.A process for producing heat comprising condensing the composition ofclaim 1 in the vicinity of a body to be heated, and thereafterevaporating said composition.
 10. A refrigeration, air-conditioning,heat pump, or chiller system containing the composition of claim
 1. 11.A composition consisting of: a. at least one fluoroolefin selected fromthe group consisting of HFC-1225ye, HFC-1234yf, HFC-1234ze, andRFC-1243zf; b. an effective amount of a stabilizer consisting of: i. atleast one compound selected from the group consisting of an epoxide anda fluorinated epoxide represented by Formula A, wherein each of R²through R⁵ is H, alkyl of 1 to 6 carbon atoms, or fluoroalkyl of 1 to 6carbon atoms with the proviso that at least one of R² through R⁵ is afluoroalkyl group;

 and ii. at least one organophosphate; and c. a hydrocarbon.
 12. Thecomposition of claim 11, wherein said hydrocarbon is selected from thegroup consisting of propane, n-butane, isobutane, cyclobutane,n-pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane,2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane,3-methylpentane, cyclohexane, n-heptane, and cycloheptane.
 13. A processfor producing cooling comprising condensing the composition of claim 11and thereafter evaporating said composition in the vicinity of a body tobe cooled.
 14. A process for producing heat comprising condensing thecomposition of claim 11 in the vicinity of a body to be heated, andthereafter evaporating said composition.
 15. A refrigeration,air-conditioning, heat pump, or chiller system containing thecomposition of claim
 11. 16. A composition, consisting of at least onefluoroolefin and an effective amount of a stabilizer consisting of: a.at least one compound selected from the group consisting of an epoxideor a fluorinated epoxide represented by Formula A, wherein each of R²through R⁵ is H, alkyl of 1 to 6 carbon atoms, or fluoroalkyl of 1 to 6carbon atoms with the proviso that at least one of R² through R⁵ is afluoroalkyl group;

b. at least one compound selected from the group consisting oforganophosphates; a lubricant selected from the group consisting ofmineral oils, alkylbenzenes, polyalphaolefins, silicone oils,polyoxyalkylene glycol ethers, polyol esters, polyvinylethers andmixtures thereof; and a hydrocarbon.
 17. A refrigeration,air-conditioning, heat pump, or chiller system containing thecomposition of claim 16.